Adsorption and Detection of Hazardous Trace Gases by Metal-Organic Frameworks

REVIEW
Air Purification www.advmat.de
Adsorption and Detection of Hazardous Trace Gases

by Metal–Organic Frameworks
Michelle Woellner, Steffen Hausdorf, Nicole Klein, Philipp Mueller, Martin W. Smith,
and Stefan Kaskel*
development for an ever increasing popu-

The quest for advanced designer adsorbents for air filtration and monitoring lation. In such buildings, accumulation
hazardous trace gases has recently been more and more driven by the need of gaseous toxicants is a critical issue,
to ensure clean air in indoor, outdoor, and industrial environments. How to especially if it is exacerbated by enhanced
increase safety with regard to personal protection in the event of hazardous gas internal heat and air regeneration systems.
The degassing of modern materials such
exposure is a critical question for an ever-growing population spending most
as plastics,[2] plywoods,[2,3] or floorings[2,4,5]
of their lifetime indoors, but is also crucial for the chemical industry in order to gives rise to the concentration of harmful
protect future generations of employees from potential hazards. Metal–organic components, e.g., formaldehyde or other
frameworks (MOFs) are already quite advanced and promising in terms of volatile organic compounds (VOCs),[6]
capacity and specific affinity to overcome limitations of current adsorbent inside buildings, and also in the cabin air
of vehicles. Emissions of VOCs and semi-
materials for trace and toxic gas adsorption. Due to their advantageous fea-
volatile organic compounds,[6] as well as
tures (e.g., high specific surface area, catalytic activity, tailorable pore sizes, their resulting impact on human health,
structural diversity, and range of chemical and physical properties), MOFs offer are a major environmental concern.[7,8]
a high potential as adsorbents for air filtration and monitoring of hazardous To enhance people’s every day comfort
trace gases. Three advanced topics are considered here, in applying MOFs for and safety, air filtration by chemical or
selective adsorption: (i) toxic gas adsorption toward filtration for respiratory physical sorption has been shown for many
years to be a key technology. Using func-
protection as well as indoor and cabin air, (ii) enrichment of hazardous gases
tional materials such as activated carbons
using MOFs, and (iii) MOFs as sensors for toxic trace gases and explosives. and zeolites, many challenges in regard to
air filtration of hazardous vapors can be
overcome. Nevertheless these technolo-
1. Introduction gies have a number of shortcomings or limitations including
limited adsorption capacity and selectivity, toxic end prod-
Adsorption and detection of toxic, or more generally, hazardous ucts, and high energy costs for regeneration.[9,10] For instance,
substances, usually at trace gas levels, has attracted major atten- impregnated activated carbons have been used traditionally in
tion in different areas, not just in respiratory protection. Accu- chemical, biological, radiological, and nuclear (CBRN) filters
mulated toxic gases and vapors are also present for indoor living, and provide excellent broad band protection against the types of
cabin air quality of vehicles or airplanes, and safety issues in chemicals described above. The carbons used in current military
public buildings. Modern life- and workspaces force mankind to filters are typically “impregnated” with metal (e.g., copper, zinc,
spend an ever increasing time in closed buildings and vehicles, molybdenum, silver, etc.) for removal of volatile chemicals such
in some cases up to 90% of their lifetime.[1] Low-energy archi- as hydrogen cyanide and cyanogen chloride. Although effec-
tecture and energy-efficient buildings are the key to sustainable tive, these impregnated metals reduce the physical adsorption
capacity of the carbon and are susceptible to ageing effects fol-
M. Woellner, Dr. N. Klein, Prof. S. Kaskel lowing long-term exposure to high relative humidity for chemi-
Fraunhofer Institute for Material and Beam Technology IWS cals such as the nerve agents.[11] In an effort to further improve
Winterbergstr. 28, 01277 Dresden, Germany protection, or to produce smaller lighter filters with lower
M. Woellner, Dr. S. Hausdorf, Dr. P. Mueller, Prof. S. Kaskel breathing resistance, alternative adsorbents are desirable.
Department of Inorganic Chemistry I
Dresden University of Technology Filtration is a very important aspect for the elimination of
Bergstr. 66, 01069 Dresden, Germany toxic gases, but an awareness of when filtration is needed is at
E-mail: stefan.kaskel@tu-dresden.de least as important. Detection of indoor and cabin air pollutants
M. W. Smith is an area of increasing interest for chemical sensors. One driver
Defence Science & Technology Laboratory is the increased demand for safety, not only in public buildings
Porton Down, Salisbury SP4 0JQ, UK
but also in private homes. In addition, security is playing an
The ORCID identification number(s) for the author(s) of this article increasingly important role, especially for public buildings, i.e.,
can be found under https://doi.org/10.1002/adma.201704679.
the detection of explosives and toxic gases. Therefore, sensing
DOI: 10.1002/adma.201704679 devices for the high variety of hazardous gases are needed.
Adv. Mater. 2018, 30, 1704679 1704679 (1 of 27) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de
Advanced sensor characteristics like sensitivity, selectivity,

and response time play a major role. To achieve sufficiently Stefan Kaskel studied
low sensor detection limits is even more challenging for haz- chemistry and received his
ardous gases due to the low concentrations (usually at ppm or Ph.D. in Tübingen (1997).
ppb level) at which they are already dangerous to health. To After a postdoctoral stay in
overcome cross-sensitivity issues, especially for the molecules the group of J. D. Corbett,
which have very similar structural properties but differ much he obtained his habilitation
in their effect on human health, intense ongoing research is degree at Bochum University
in progress to improve existing and new sensor devices. The on the design and function-
majority of available sensors rely upon organic-polymeric or ality of new porous materials
inorganic-semiconductor thin films that adsorb (physisorption (2003). At the same time,
or chemisorption) or react with the analyte molecules. Changes he was a group leader at the
in electrical, photophysical, or mechanical properties are mon- Max Planck Institute for Coal
itored. In order to be able to reliably detect trace target com- Research from 2002 to 2004. Since June 2004, he has been
pound concentrations, gas preconcentration, i.e., enrichment, a Professor of Inorganic Chemistry at Dresden University
can be applied. Using high surface area functional materials, of Technology, and from 2008 onward, also the head of the
trace gases can be enriched over a certain period of time fol- business unit Chemical Surface and Reaction Technology at
lowed by a thermal desorption, which generates a short intense the Fraunhofer-Institute for Material and Beam Technology.
pulse of higher gas concentration. Using preconcentrators,
sensor sensitivity can be tuned to lower detection limits and
selectivity can be enhanced due to the specific pore size and
2. Common Trace and Toxic Gases
pore surface environment within the framework (e.g., polar/
nonpolar inner surface), leading to a refinement of analyte size Maximum values for a large number of toxic industrial chemi-
(e.g., molecular sieving), and/or analyte-framework interaction. cals (TICs) are given by the Air Quality Guidelines for Europe
Advanced sensor systems would allow localized prediction of published by the World Health Organization (WHO).[17]
hazardous gases, e.g., for early warning against terrorist threats For noncarcinogenic substances, stress thresholds are
with explosives and chemical warfare agents (CWA). given, below which a significant risk for people’s health is
To solve such challenges, metal–organic frameworks (MOFs) not expected. These values are calculated from known lowest
offer many advantageous features including high specific observed adverse effect levels, and/or no observed adverse
surface area, enhanced gas/vapor adsorption, high catalytic effect level, divided by a protection factor. In some cases,
activity, and tailorable pore sizes and functionality.[12–14] They where a concentration below any health-adverse limit causes
are very well known for their structural diversity as well as their unpleasant smells, odor limits are described. Varying values are
range of chemical and physical properties. Therefore, MOFs listed for the same pollutant, depending on variable exposure
can be used as excellent adsorbent materials to filter, enrich, times typical for different exposure situations. Carcinogenic
and sense diverse toxic or hazardous gases. With this in mind, substances can cause cancer regardless of the concentration. In
several extensive reviews, such as those by
Barea et al.[15] and DeCoste and Peterson[9]
in 2014, and most recently Bobbitt et al.[16]
in 2017, have highlighted the potential of
MOFs for filtration of toxic chemicals. It is
not intended to replicate the details of those
reviews here, rather to explore the depth
of current knowledge of the use of MOFs
against harmful gases.
Here, we focus on three main topics in
regard to hazardous gases (Figure 1). One
focus is the adsorption of toxic organic and
inorganic gases with regard to filtration for
respiratory protection (this is a minor part
due to other recently published reviews on
that topic[9,15,16]), indoor and cabin air. In
addition to the filtration aspect, MOFs as
sensors for toxic trace gases and explosives
are reviewed as well as the enrichment of
hazardous gases using MOFs and the high
variety of structural MOF properties which
can be utilized to enhance the sensitivity and
selectivity of already established and new Figure 1. Schematic overview of this review in regard to filtration, enrichment, and sensing
sensor devices. applications of the MOFs for hazardous gases.
this case, “life time risks” are given instead of thresholds. The organic compound having an initial boiling point less than or
lifetime risk is the statistical probability of developing cancer equal to 250 °C measured at a standard pressure of 101.3 kPa.”
caused by long-term exposition to a well-defined concentration It is very common to judge the indoor VOC concentration as
of the substance during lifetime. “total volatile organic compounds, TVOC” with respect to the
These guidelines are incorporated into national laws, stand- technical feasibility of measurements in parts per million (ppm)
ards, and guidelines, not only in Europe (e.g., the indoor guide- range.[19,20] A TVOC average concentration below 0.2 mg m−³
lines of the Federal Environment Ministry, Germany),[18] but also is assumed to affect neither health nor general well-being and
in the US (e.g., the publication “Building Air Quality—a guide for provides a challenging target for filter materials.[20]
Building Owners and Facility Managers”[19] of the National Insti- Another field of filter application is CBRN filtration for extreme
tute for Occupational Safety and Health, NIOSH). An air condi- situations, like industrial accidents or terrorist attacks. The CBRN
tioner filter for buildings or cars should be capable of reducing filtration has been an exclusive domain of the military. How-
the concentrations of toxic components at least below the given ever, the increasing prevalence and ever present threat of CWA
limits. Table 1 gives some examples of these WHO guidelines. use, as well as the more easily available TICs, has broadened the
Organic compounds with measurable vapor pressures are interest in such filters.[21] Many commercially available filters for
referred to as VOCs. A precise definition of VOC is given in use against toxic gases are certified against the NIOSH standards.
the directive 2004/42/CE of the European Parliament as “any As an example, the NIOSH Standard for CBRN full facepiece air
purifying respirators (APR) specifies performance levels against
ten representative chemicals, as shown in Table 2 below.[22]
Table 1. Examples of exposure limits for different TICs given by WHO
guidelines.[17] In a similar way, the equivalent European Standard (DIN
EN 14387, DIN = Deutsches Institut für Normierung, [German
Chemical Guideline value (time if indicated) Institute for Standardization]; EN = European Standard)[23] spec-
ifies performance levels against ammonia, cyclohexane, chlo-
Inorganic pollutants
rine, hydrogen sulfide, hydrogen cyanide, and sulfur dioxide.
Carbon monoxide 100 mg m−3 (15 min) With the exception of chlorine, which is not explicitly covered
60 mg m−3 (30 min)
in the NIOSH standard, these all replicate chemicals are listed
30 mg m−3 (1 h)
in Table 2. However, the specification of concentrations and pro-
10 mg m−3 (8 h)
tection times is handled differently in each standard.
Hydrogen sulfide 0.15 mg m−3 (24 h, health limit)
Beyond the detection and separation of CWAs or VOCs, the
7 µg m−3 (30 min, odor limit)
detection of explosives is also a challenging task. Critical prop-
Nitrogen dioxide 200 µg m−3 (1 h) erties of explosives are pressure sensitivity, impact sensitivity or
40 µg m−3 (annual) spontaneous combustion. The class of explosive agents is highly
Sulfur dioxide 500 µg m−3 (10 min) diversified, and most explosives are based on nitrocompounds.
20 µg m−3 (24 h) They can be divided in different groups due to their organic back-
Ozone 100 µg m−3 (8 h, daily maximum) bones: (i) aromatic structure such as 2,4,6-trinitrotoluene (TNT),
Organic pollutants picric acid (2,4,6-trinitrophenol, TNP) or N-methyl-N-2,4,6-
tetranitroanilin (tetryl); (ii) aliphatic backbones such as nitroglyc-
Acrylonitrile Carcinogenic, life time risk 2 × 10−5 at 1 µg m−3
erin, pentaerythritol tetranitrate (PETN) or (iii) cyclic backbones
Benzene Carcinogenic, life time risk
like hexahydro-1,3,5-trinitro-1,3,5-triazin (hexogen, RDX), and
10−4 at 17 µg m−3
cyclotetramethylene tetranitramine (octogen, HMX). Also explo-
10−5 at 1.7 µg m−3
6 × 10−6 at 1 µg m−3
sive agents with a large percentage of inorganic components such
10−6 at 0.17 µg m−3 as gunpowder or ammonium nitrate fuel oils (ANFO) are known.
ANFOs are a physical mixture of ammonium nitrate and mineral
Carbon disulfide 100 µg m−3 (24 h, health limit)
−3
20 µg m (30 min, limit for viscose emissions) Table 2. Canister test challenge and test breakthrough concentrations.[22]
1,2-Dichloroethane 0.7 mg m−3 (24 h)
Dichloromethane 3 mg m−3 (24 h) Chemical Test concentration Breakthrough concentration
0.45 mg m−3 (weekly) [ppm] [ppm]
Formaldehyde 0.1 mg m−3 (30 min) Ammonia 2500 12.5
Styrene 70 µg m−3 (30 min) Cyanogen chloride 300 2
Tetrachloroethylene 0.25 mg m −3 Cyclohexane 2600 10
Toluene 1 mg m−3 (30 min) Formaldehyde 500 1

0.26 mg m−3 (weekly) Hydrogen cyanide 940 4.7 (sum of HCN and (CN)2)
Trichlorethylene Carcinogenic, life time risk Hydrogen sulfide 1000 5.0
10−4 at 230 µg m−3
Nitrogen dioxide 200 1 ppm NO2 or 25 ppm NO
10−5 at 23 µg m−3
10−6 at 2.3 µg m−3 Phosgene 250 1.25
4.3 × 10−7 at 1 µg m−3 Phosphine 300 0.3
Vinyl Chloride Carcinogenic, life time risk 1 × 10−6 at 1 µg m−3 Sulfur dioxide 1500 5
Table 3. Workplace concentrations of selected explosives.[24–30]
Chemical NOISH REL [mg m−3] OSHA PEL [mg m−3]

TNT 0.5 1.5
Picric acid 0.1 0.1
Nitroglycerin 0.1 2
RDX 1.5 1.5
HMX not established not established
oil or diesel and hence are very cheap. There are also explosives
without nitro groups such as triacetone triperoxide (APEX, TATP),
which is often used by terrorists because of a cheap and easy syn-
thesis route. Maximum allowable concentrations of explosives are
given by different institutions, like NIOSH or the Occupational
Safety and Health Administration (OSHA) (Table 3). Figure 2. Scheme of a breakthrough measurement. Elution of the test gas
(c0 as initial concentration) through the adsorption column (blue) and
resulting breakthrough curve.
3. Methodological Aspects: From Rapid Screening
(climit) limit is detected in the exhaust, the breakthrough point is
to Demonstrators and Performance Assessment
reached. The time or capacity at this point normally defines the
3.1. Testing Methods filter performance. If the breakthrough measurement is con-
tinued, the concentration increases until the initial test gas con-
The adsorption capacity is a crucial property of a potential mate- centration (c0) is reached by means of complete saturation of the
rial for air pollutant removal or sensing applications. A common adsorber. Breakthrough experiments are established for testing
characterization method for the evaluation of filter media is static filter materials in respiratory protection (e.g., DIN EN 14387,[23]
physisorption. Adsorptive pulses are dosed to the material at a ASTM D6646 - 03(2014) (ASTM = American Society for Testing
defined temperature and the uptake is measured volumetrically or Materials)[35]) or cabin air filtration (e.g., ISO 11155-2:2009 (ISO =
gravimetrically as a function of pressure (adsorption isotherm[31]). International Organization for Standardization).[36]
Porous materials are usually characterized by specific surface area, However, established static physisorption and dynamic break-
pore volume or pore size distribution which is obtained by nitrogen through experiments can be time-consuming (the evaluation of
physisorption at 77 K. Beside general adsorbent properties, the a potential material can take several hours) and costly, and may
adsorption capacity of a specific adsorptive can be determined by require a large amount of material (both adsorbent and adsorp-
static physisorption experiments. In this regard, the adsorption tive). Due to the rapid development in MOF synthesis in the last
behavior at very low pressures (p/p0 ≪ 0.1) is relevant for trace years, a wide variety of materials are available with an associated
gas adsorption at ppm or ppb concentration levels. The type of the requirement for fast screening methods to select materials for a
isotherm plays an important role in material evaluation. Indeed, potential application. To speed up this evaluation significantly,
a type I isotherm is preferable for the adsorption of very low con- optical calorimetry is a valuable novel technique. This new tech-
centrations, for instance for filtration or enrichment. However, it nology is based on the optical detection of a temperature change
can be challenging to measure the adsorption isotherms for cer- of a sample due to the released total heat during adsorption of a
tain relevant chemicals (e.g., formaldehyde, ammonia), especially certain test gas. Only a few minutes of detection time are needed
in the application relevant ppm region. Static physisorption experi- to assess the materials performance. The experimental setup of
ments give an equilibrium load at a certain temperature and pres- the optical calorimeter “InfraSORP” is shown in Figure 3a. The
sure and in some cases information on the adsorption kinetics sample is exposed to a test gas flow at ambient conditions (298 K,
(e.g., using magnetic suspension balances[32]). Furthermore, 1 atm). The adsorption-induced temperature increase is detected
isotherm measurements in standard equipment are limited to by an infrared temperature sensor. It was recently shown that
single-component analysis. Multicomponent techniques exist but the specific integral of the thermal response (Figure 3b) can be
are only to a limited extent commercially.[33,34] Especially for real correlated to the specific surface area or the adsorption capacity
filter or sensing applications, the test of potential materials under over a wide range of materials. Furthermore, the shape of the
dynamic conditions and multigas adsorption (test gas mixtures, thermal response provides information on adsorption kinetics.
presence of humidity) is mandatory. In common breakthrough Sandra et al. investigated the H2S performance of a MOF com-
experiments, the adsorber is continuously exposed to an adsorptive posite by breakthrough experiments and successfully reproduce
flow at a specific temperature and pressure which reflects a single the results with optical calorimetric tests. Hence it is apparent
point on the adsorption isotherm. The exhaust gas concentration that optical calorimetry is a rapid, simple, and cost-effective sup-
is detected, e.g., by chemical sensors or infrared (IR) spectroscopy plement to commonly used breakthrough and physisorption
and correlated against the time (breakthrough curve, Figure 2). methods for a wide variety of samples and adsorptives.[37–40]
The test gas begins to adsorb at the inlet of the column and A standard method for detection of toxic chemicals in ambient
elutes through the adsorber. When a predetermined concentration air is the adsorption in sorbent tubes and subsequent analytical
Figure 3. a) Experimental setup of the optical calorimeter InfraSORPone and b) thermal response signal of an activated carbon sample (AC7), which is
exposed to a test gas flow of 70 cm3 min−1n-butane at ambient conditions. Reproduced with permission.[41] Copyright 2017, Springer.
thermal desorption (TD) with coupled gas chromatography (GC) development of potential materials for toxicant removal, enrich-
and optional mass spectrometry (MS), e.g., DIN ISO 16000-6, ment, and their use for sensing applications.
ISO 16017-2:2003(en).[42,43] One or more components of interest
are collected on the adsorber in the sorption tube and released
to the detection unit by continuous purging and simultaneous 3.2. Scale-Up and Shaping of MOFs for Filter Demonstrators
heating. Especially in the field of trace gas detection, TD is a
common method for preconcentration prior to GC injection. Scale up and shaping of MOFs is a crucial requirement for
Often the sensitivity of sensors is insufficient to detect trace industrially relevant applications such as toxic gas and air fil-
gases and vapors in real time and, therefore, preconcentrators are ters. Not only academic research groups but also an increasing
essential for detecting toxic substances. Typically porous mate- number of MOF “startup companies” are focusing on eco-
rials are used as preconcentration media, bringing the detection nomic and ecological synthesis, upscaling and shaping of the
limit down to the desired level (Figure 4). Porous polymers such MOF materials. Due to the large number of the MOF struc-
as TenaxTA and activated carbons are very well known to be used tures that have been published (several thousand[44]), it is of
for gas enrichment. A more detailed discussion on concentrators course impossible to provide all of them in a relevant amount
is given in Section 5. The principle of sorbent tubes is also used and shape for market driven applications. On the one hand
in the field of gas detection tubes. Various gas detection tubes there are many MOF syntheses which start from a very com-
are available for a wide range of toxicants, e.g., H2S, NH3, CO plex and multistep linker synthesis but on the other hand there
(e.g., Dräger, RAE Systems). The toxicant reacts with the mate- are already many linker molecules commercially available. For
rial in the detection tube by, e.g., oxidation or pH reaction under example, terephthalic acid, a linker of very well-known MOFs like
a visible color change. However, despite the simplicity of the test, MOF-5 (Zn4O(bdc)3, bdc = benzene-1,4-dicarboxylate), MIL-101
the presence of a complex matrix or chemically similar compo- (Cr3O(OH)(H2O)2(bdc)3), MIL-53 (Al(OH)(bdc)), UiO-66
nents, e.g., different alcohols, limit the use of detection tubes (Zr6O4(OH)4(bdc)6), is produced in several million tons per
and a classical analysis in laboratory is mandatory. year.[45] Trimesic acid (e.g., Hangzhou Rebtech Novel Material
Depending on the test requirements (static/dynamic, single- Co., Ltd.: 0.1–0.2 $/kg (Alibaba 10/2017))[46] and fumaric acid
component/multigas, humidity, temperature, concentration, (Anhui Leafchem Co., Ltd.: 0.85–1 $/kg (Alibaba 10/2017)[47]),
etc.) as well as available time and apparatus resources, a the linker compounds of HKUST (Hong Kong University of
huge variety of testing methods is available to support the Science and Technology)-1 (Cu3(btc)2, btc = benzene-1,3,5-tri-
carboxylate), and Al-fumarate are also avail-
able in ton amounts for prices of a few US
dollars per kilogram.
If the starting materials for MOF synthesis
are available, scalability is the most important
question that arises if industrially relevant
applications are to be tested.[48] The initial
synthesis and discovery of new MOFs is usu-
ally performed on a very small scale, often
using toxic solvents with low yields. These
first experiments allow for a characterization
of the MOF in regard to porosity or crystal
structure. However, in contrast to single
crystal synthesis, powders of a similar MOF
Figure 4. Strategy for preconcentration for sensing application using a porous material. can be produced in many different ways.
Although MOF-5 undergoes structural degradation under solution of the linker compound. From the ecological point of view
moist conditions and is not usable for filter applications in the advantage of this method is that there is no waste problem
ambient air, it is among the earliest and most studied MOFs with remaining anions from a metal salt in the mother solution.
and is intended to serve as an example for MOF synthesis devel- Other examples for high space time yield methods are spray
opment. However, several MOFs exist which are stable under drying[58] and flow chemistry[59] (continuous flow reactions),
moisture and hence are well-suited for application at ambient showing that there is no general difference in the feasibility of
conditions. Several studies were done in this field, e.g., in a MOF production compared with the production of other chem-
review by Burtch et al.[49] MOF-5 was synthesized in the earliest ical products synthesized in ton amounts.
publication in 1999 by a slow diffusion process.[50] Zinc nitrate An excellent overview to date about industrial and semi-
and terephthalic acid were used as starting materials, N,N- industrial scale MOF syntheses, general methods and space
dimethylformamide (DMF) as solvent and trimethylamine as time yields are given by Rubio-Martinez et al.[60]
base. This method was followed by a solvothermal reaction in The powdery nature of MOFs produced with high yield
2002, using the same starting materials, but with N,N-diethylfor- methods is problematic for most filter applications due to a high
mamide (DEF) as solvent.[12] In 2008, the same group published pressure drop in columns and filters, and the emission of dust. A
a synthesis route as simple precipitation reaction, starting from shaping process, bringing the powders in granular form, such as
zinc acetate, giving a powder with the same porosity properties it is state-of the-art in zeolite production, is necessary. However,
as the single crystals before.[51] Using basic acetates, containing the temperatures used to harden the mineral binder materials
the inorganic nodes as preformed clusters, it was possible to used in zeolite production, e.g., 720 °C for zeolite NaX,[61] cannot
switch from toxic formamide solvents to acetone, and to synthe- be used for MOFs because of their organic nature and rather low
size MOF-5 analogs containing metals other than zinc.[52] Now, decomposition temperatures. A smart way to bypass this problem
MOF-5 can be produced in high yields by a solvent assisted is published by Ren et al., by adding sucrose as a binder mate-
phase transition of a nonporous zinc terephthalate phase.[53] rial to the MOF slurry, shaping the material by using a pelletizer
Another prominent example is MIL-100(Fe) and drying it at low temperature.[62] Another method of forming
(FeIII3O(H2O)2F∙(btc)2∙nH2O), which has the same network pellets or shaped bodies is binderless pressing of MOF pow-
topology as MIL-101(Cr). The synthesis of MIL-100(Fe) was first ders. Bazer-Bachi et al. have shown the influence of the applied
reported in 2007 using a highly diluted hydrothermal reaction mechanical pressure at forming pellets of three different MOFs:
at 150 °C with the addition of HF. These reaction conditions ZIF-8 (ZIF = zeolitic imidazolate framework), SIM-1 (SIM = sub-
were too demanding to achieve an industrial commercializa- stituted imidazolate material), and HKUST-1. SIM-1 has the same
tion.[54] However, recently an ultrahigh yield solid state reaction sodalite (SOD) topology as ZIF-8, but has additional aldehyde
was reported, producing the same MOF simply by heating iron functions on its imidazole linker molecules. They found signifi-
nitrate or chloride together with trimesic acid.[55] cant differences in their stabilities against pressure-induced amor-
BASF performed the first industrial scale space time yield phisation associated with porosity loss. ZIF-8 loses only 10% of
optimization for a few MOF compounds in the early 2000s.[48] surface area and crystallinity being compressed with 18 kN. SIM-1
Space time yields between 20 and 300 kg m−3 d−1, compared and HKUST-1 lose about 30% and more than 75%, respectively
with 50–150 kg m−3 d−1 for industrially produced zeolites are of their initial surface area after the application of only 5 kN as
reported. The products of these test productions were provided by pelletization pressure.[63] Other alternative shaping and/or integra-
Sigma-Aldrich as BASOLITE and BASOSIV materials.[56] A very tion methods are published too, e.g., processing MOFs into paper
promising electrochemical method for producing HKUST-1[57] sheets,[64] fibers,[65] membranes,[66,67] foams[68] or coatings.[69]
is used, based on the anodic dissolution of copper metal in a Some examples for the shaped MOFs are shown in Figure 5.
Figure 5. Examples of shaped MOFs. a) HKUST-1 monolith; b) Zr-MOF pellets; c) UTSA-16(Co) monolith; d) MIL-100(Fe)@xerogel composites; e)
HKUST-1 membrane. a) Reproduced with permission.[72] Copyright 2010, The American Ceramic Society. b) Reproduced with permission.[62] Copyright
2015, Elsevier. c) Reproduced with permission.[71] Copyright 2016, Elsevier. d) Reproduced with permission.[70] Copyright 2015, Elsevier. e) Reproduced
with permission.[65] Copyright 2012, Royal Society of Chemistry.
Shaping and granulation of MOFs is extensively reviewed by reported to date (>12 mmol g−1) and they also appear to be stable
Lee et al. in a chapter of the book “The Chemistry of Metal– toward repeated adsorption/desorption cycling of ammonia.
Organic Frameworks.”[73] They listed not only different shaping
methods but also mechanical strength and porosity losses.
4.1.2. Chlorine
4. Adsorptive Removal of Toxic Gases by MOFs Chlorine was the first chemical weapon used in modern times,
on the battlefields of Ypres in World War 1.[78,79] Fully one hun-
for Filter Application
dred years on, its repeated use in the Syrian conflict reinforces the
4.1. Inorganic Adsorptives potential threat from this readily available chemical.[80,81] In view of
this, it is perhaps surprising that there are relatively few reports of
4.1.1. Ammonia the use of MOFs to filter chlorine from contaminated airstreams.
In their 2008 study of MOFs for removal of harmful
The use of MOFs to remove ammonia has been extensively chemicals, Britt et al. found that five of the six MOFs studied
reviewed elsewhere, and the content of those reviews has not exhibited lower capacities for chlorine than BPL carbon (only
been repeated in detail here.[9,15,16] DeCoste and Peterson[9] IRMOF-3 (IRMOF = isoreticular metal–organic framework)
concluded that the best performing MOFs typically had either (Zn4O(NH2-bdc)3, NH2-bdc = 2-amino-1,4-benzenedicarboxy-
coordinatively unsaturated metal sites or organic linkers which late) was higher).[10,56] Barea et al. noted that open metal sites
could chemically bind to ammonia. In addition, they tended to tend to be ineffective for this chemical, as chlorine does not act
have large micropore volumes to facilitate this interaction. as a ligand.[15]
A further possible mechanism for ammonia removal was In view of this, DeCoste et al. showed that ligand function-
recently reported by Wilcox et al., who supported hydrochloric and alization gave scope for removing chlorine, as demonstrated
formic acid (FA) on an aluminum porphyrin based MOF which with amine functionalized UiO-66 (University of Oslo-66). A
showed remarkable stability toward acid uptake as shown by chlorine capacity of 1.24 g g−1 is reported (at dry conditions).
powder X-ray diffraction and nitrogen adsorption. The acids were Chlorine is removed by an electrophilic aromatic substitution
strongly bound to the MOF and showed significant capacity for reaction mechanism by the linker, with following reaction of
ammonia removal in both the parent MOF and activated carbon HCl with the secondary building unit and/or the formation of
(BPL carbon by Calgon Carbon Corporation Pittsburgh, Pennsyl- a NH3+ functionality and Cl− as counter ion.[82] In 2017, this
vania). While Al2(OH)2(H2TCPP) (named as Al-PMOF, TCPP = work was extended by Browe et al., looking at an “engineered”
tetra(4-carboxyl-phenyl) porphyrin) has an ammonia breakthrough (20 × 40 American Society for Testing and Materials (ASTM)
uptake of 0.5 wt% under dry conditions and 500 ppm ammonia US Standard Mesh granules) version of the same MOF for
(initial concentration), the ammonia uptake was increased by a filtration of chlorine and hydrogen chloride.[83] The results
factor more than eight by acid support (Al-PMOF-HCl: 4.6 wt%, showed that although compaction (to form granules) reduced
Al-PMOF-FA: 3.8 wt%). An additional increase in ammonia uptake the surface area of the materials, the engineered MOF was still
was exhibited in the presence of water with a maximum break- able to outperform a commercially available impregnated acti-
through capacity of 7.9 wt% for Al-PMOF-HCl.[74] vated carbon against these two chemicals. While UiO-66-NH2
Bobbitt et al.[16] reviewed recent reports of mixed and/or (Zr6O4(OH)4(NH2-bdc)6) has a chlorine capacity of 0.062 g g−1
composite filtration media containing MOFs, and also sum- in regard to OSHA PELs (1 ppm Cl2) the carbon reaches a chlo-
marized research to model the interaction of ammonia with rine loading of 0.054 g g−1.
MOFs, in order to identify optimum materials. Among these The same group has also reported the use of the same MOF,
latter studies is the work of Kim et al., who modeled a wide incorporated into electrospun nanofiber mats (“MOFabric”), for
range of metal catecholates, which could potentially be incor- chlorine removal.[84] Chlorine loadings were consistent with the
porated as linkers within MOFs.[75] Out of the various func- amount of MOF in the fabric swatches, showing that the MOF
tionalities considered, RCOOCu groups were calculated to remained accessible. Materials of this type offer scope for the
have the highest binding energy with ammonia. In response use of MOFs not just for respiratory protection but also in pro-
to this, Joshi et al. have recently reported the synthesis of tective clothing.
a series of functionalized UiO-66 MOFs containing copper
carboxylate groups.[76] The materials showed high ammonia
removal capacities under both dry and humid conditions and 4.1.3. Cyanogen Chloride
retained the framework structure. The highest ammonia break-
through capacities are obtained for UiO-66-(COOCu)2 with On current military carbons, cyanogen chloride is removed
6.38 mmol g−1 under dry conditions and 6.84 mmol g−1 in the through reaction with metal impregnants[85] and, in some cases,
presence of humidity. This work provides an excellent example the organic amine triethylene diamine.[86] Relatively few reports
of the interaction between the modeling and experimental of the interaction of MOFs with this chemical are known, but
communities, leading to materials with enhanced performance in 2011 Glover et al. showed that MOF-74 (M2(dhtp)(H2O)2,
over those tested previously. dhtp = 2,5-dihydroxyterephthalate) analogs were able to remove
The limits of ammonia removal by MOFs continue to be cyanogen chloride from a dry airstream.[87] However, competi-
extended, as notably shown in the 2016 work by Rieth et al.[77] tion with water vapor meant that performance was poor in a
The ammonia uptakes of these materials are among the highest humid airstream. In 2013 Peterson et al. reported data for
UiO-66-NH2 in powder and pelletized form.[88] The latter was MOF-74 series, the majority of phosphine uptake takes place
compared to a typical broad spectrum carbon, and performed up to 0.006 bar, unlike the uptake in the activated carbon.
poorly, mainly due to mass transfer kinetic limitations. In particular, MOF-74(Co) and MOF-74(Mn) show the
highest phosphine loadings at 0.006 bar with 6.30 and
5.05 mmol g−1. In contrast, the capacity of activated carbon at
4.1.4. Hydrogen Sulfide 0.9 bar is only 4.37 mmol g−1. Relatively little data is available
on this chemical, either for the MOFs or other adsorbents, pos-
The use of MOFs to filter H2S has been reviewed previously, sibly due to the hazards involved with handling it in the labora-
most recently by Bobbitt et al.[16] Typically, H2S will bind to open tory (e.g., it is pyrophoric).[95]
metal sites, such as those in the extensively reported HKUST-1,
resulting (in that case) in breakdown of the MOF structure and
the formation of copper sulfide. Interestingly, several composites 4.1.7. Arsine
of this MOF have shown apparently synergistic effects, including
the graphite oxide/MOF composites reported by Bandosz and Arsine is often regarded as a CWA and is used industrially as
co-workers[89] and also the MOF/activated carbon composites dopant for the semiconductor industry. There are only a few
reported by Shi et al.[90] In the latter study (reported in 2017 and publications which deal with arsine removal by MOFs.
hence not described in the aforementioned reviews), incorporation Peterson et al. investigated HKUST-1 for arsine capture.
of less than 2% of activated carbon into the composites resulted Micro-breakthrough experiments demonstrated a higher arsine
in a 51% increase in H2S uptake; this was attributed to increased uptake of HKUST-1 in comparison to a carbon adsorbent under
microporosity and availability of copper sites for reaction. humid and dry conditions. However, less arsine retention is
identified under packed bed conditions. The reason for that
is inhibited mass transfer by pore blocking due to the large
4.1.5. Nitrogen Dioxide, Nitrogen Oxide, and Sulfur Dioxide arsenic molecules and the formation of arsenic trioxide at the
copper sites.[96]
The removal of nitrogen and sulfur oxides has been reviewed exten- In 2005, a patent appeared which addressed the electronic
sively elsewhere.[9,15,16] In 2008, Britt et al. reported low capacities gas storage, including arsine, on MOFs. Grand Canonical Monte
for SO2, with the exception of MOF-74.[10] DeCoste and Peterson Carlo (GCMC) simulations show an increasing arsine uptake
commented in their review that most MOFs do not provide the with increasing pore size, pore volumes, and gravimetric sur-
necessary chemistry for SO2 reaction, especially since it does not face area in the UiO-MOF series. While UiO-66 (8 and 10 Ǻ,
bond to coordinatively unsaturated metal sites. Similarly, removal 0.13 cm3 g−1, 1680 m2 g−1) reaches an arsine adsorption capacity
of NO2 tends to be dependent on a combination of physical adsorp- of 70 g L−1, a maximum capacity of 775 g L−1 is shown by UiO-68
tion and/or interaction with functional groups on the MOF linkers. (Zr6O4(OH)4(tpdc)6, tpdc = terphenyl-4,4″-dicarboxylate) (8 and
In contrast, NO does bind to open metal sites, although this can be 15 Ǻ, 1.1 cm3 g−1, 4300 m2 g−1). UiO-MOFs with larger pores
adversely affected by the presence of water vapor.[9] and higher pore volumes exhibit a decreasing arsine capacity, for
Recently, a publication by Peterson et al. showed “unpre- example UiO-4 ph with 120 g L−1. In addition, experimental data
cendented removal capacities” for NO2 using UiO-66-NH2. Fur- were reported for arsine adsorption on Zn2(bdc)2(1,4-diazabi-
thermore, the amounts of NO generated were lower than for cyclo[2.2.2]octane (dabco)). The arsine uptake was 600 mg g−1 at
other adsorbents tested (BPL carbon and UiO-66 MOF).[91] 650 Torr and 298 K. Zn2(bdc)2(dabco) removed more than 95%
High NO removal capacities can be reached by a strong interac- of arsine in a filled gas cylinder under atmospheric pressure.[97]
tion of NO with open metal sites which was previously published
for HKUST-1 and MOF-74 series.[92,93] At ambient conditions
(298 K, 1 bar), NO capacities of 3 and 7 mmol g−1 are reported 4.1.8. Radon
for HKUST-1 and MOF-74 (Co and Ni). Xiao et al. reported very
large NO capacities for HKUST-1 of around 9 mmol g−1 at low Due to its radioactive nature, exposure to radon is one of the
temperature (196 K, 1 bar), which is significantly greater than any main risks for lung cancer besides smoking. Radon and its
other adsorption capacity reported on a porous solid such as zeo- decay products enter the indoor atmosphere from soil gases and
lites.[93] The exposure to moisture results in a release of NO which groundwater beneath buildings and building materials.[98,99]
is favorable for bioapplications (from the listed publications), but It was previously shown that the radon concentration can be
not for toxic gas capture and filtration. While the NO desorption reduced by particulate air and carbon filters.[100–102] There are
of HKUST-1 is nearly irreversible with 1 µmol g−1 under moisture several GCMC simulation studies, which address radon adsorp-
exposure, MOF-74 completely releases the preadsorbed NO. tion on MOFs. An experimental investigation is demanding
because of the radioactivity.
Meek et al. investigated the effect of linker polarizability for
4.1.6. Phosphine noble gas adsorption on MOF-5 and a series of monohalogen-
ated IRMOF-2 (Zn4O(X-bdc)3, X = F, Cl, Br or I). Up to a pres-
In 2015, Weston et al. described the ability of MOFs with open sure of 0.6 atm, where the radon adsorption follows Henry’s law,
metal sites (specifically MOF-74) to adsorb phosphine. The the adsorption capacity increases with polarizability of the MOF.
capacities were shown to be significantly higher than for a A Rn/N2 adsorption selectivity of 15.1 (IRMOF-2-F) to 22.2
typical broad spectrum activated carbon.[94] Especially for the (IRMOF-2-I) is observed by comparing the Henry’s constants.
This effect inversely changes at a pressure over 0.6 atm due to a 4.2.2. Benzene
stronger tendency to saturated pore filling rather than the polar-
izability effect.[103] Higher selectivity of radon over nitrogen Saini and Pires also measured the benzene adsorption iso-
at infinite dilution is reported by Parkes et al. The best candi- therms for HKUST-1 and ZSM-5/HKUST-1 foam material
dates for radon adsorption are Nottingham-100 (NOTT-100) at room temperature.[107] A saturation capacity of 0.469 g g−1
(Cu2(bptc)(H2O)2, bptc = biphenyl-3,3′,5,5′-tetracarboxylic acid) (≈0.006 mol g−1) at 1000 Pa was found for the pure MOF
with Rn/N2 selectivity of 168, porous coordination network-14 compound. Britt et al. published breakthrough curves for
(PCN-14) (Cu2(adip), adip = 5,5′-(9,10-anthracenediyl)diisoph- benzene and other TICs, measured on six different MOFs
thalate) with 138 Rn/N2 selectivity, ZIF-8 (Zn(C4N2H5)2) with (MOF-5, IRMOF-3, MOF-74, MOF-177 (Zn4O(btb)2, btb =
112 Rn/N2 selectivity and MIL-53(Al) (Al(OH)(bdc)) with 65 1,3,5-tris(4-carboxyphenyl)benzoate), HKUST-1, IRMOF-62
Rn/N2 selectivity.[104] Recently, Wang et al. confirmed the suit- (Zn4O(dab)3, dab = diacetylene-1,4-bis(4-benzoate)), and
ability of ZIF-8 as radon capture material.[105] compared with BPL carbon.[10] They used a test concentra-
Perry et al. carried out GCMC studies of Rn adsorption on ten tion of 440 ppm benzene in N2 at 25 °C and a flow rate of
MOFs which all show a high Rn/N2 selectivity and hence, are 25 mL min−1. The highest dynamic adsorption capacity of
suggested as effective adsorbents for indoor air purification and 0.176 g g−1 was found for HKUST-1, 114% of the value meas-
decontamination. The effect of open-metal sites within a con- ured for BPL carbon.
stant topology (MOF-74(X), X = Mg, Co, Ni, Zn) as well as the The competitive adsorption of benzene and water in
effect of the pore size within similar open metal site identity and HKUST-1 is addressed in Zhao et al.[108] They published ben-
a similar coordination environment on noble gas adsorption was zene adsorption isotherms at 288, 298, 308, and 318 K with
investigated. They found out that the MOF-74(X) series has the saturation capacities of 10.16 mmol g−1 (794 mg g−1) at 288 K
lowest Rn saturation capacity followed by HKUST-1, and finally and 9.42 mmol g−1 (736 mg g−1) at 318 K. Comparing benzene
the nbo MOF series. At 1 atm, NOTT-102 (Cu2(qptc)(H2O)2, isotherms with the water isotherms measured at the same tem-
qptc = quaterphenyl-3,3‴,5,5‴-tetracarboxylate) has the highest peratures, they calculated a preference for water adsorption
Rn capacity, however it is the last of the investigated MOFs that at 288 K but a preference for benzene adsorption at 308 and
reaches the saturation point. NOTT-102 has the largest free 318 K. This is very surprising, because HKUST-1 is known as
volume of the studied MOFs, which is important at saturation a hydrophilic MOF, which binds water and other Lewis-acidic
when the MOF/adsorbate interaction is not a factor. Before satu- molecules very strongly because of free coordination sites
ration, PCN-14 shows a high radon uptake and its behavior is in the Cu2+ centers. The priority of this publication was to
similar to the gas adsorption trends of NOTT-100. For Rn at measure breakthrough curves for benzene at 13 and 34% R.H.
lower pressures, NOTT-100 and PCN-14 exhibit the greatest (relative humidity), a test gas concentration of 16.38 mg L−1
uptake but have a lower saturation volume and reach saturation (4763 ppm) at 308 K with nitrogen as carrier gas (70 mL min−1).
faster than NOTT-101 (Cu2(tptc)(H2O)2), NOTT-103 (Cu2(nddi) The dynamic benzene capacity was shown to decrease from an
(H2O)2, nddi = 5,5′-naphthalene-2,6-diyl-diisophthalate), or initial 9.01 mmol g−1 (static capacity at 308 K) under dry con-
NOTT-102, which have larger free volumes. The MOF-74(X) ditions to 8.53 mmol g−1 at 13% R.H. and 6.57 mmol g−1 at
series reach saturation at a similar pressure like NOTT-100 and 34% R.H., which corresponds to reductions of 5.3 and 27.1%
PCN-14, but at a much lower saturation volume.[106] (Figure 6).
4.2. Volatile Organic Compounds
4.2.1. Cyclohexane
Cyclohexane is included in both the NIOSH APR and EU

EN14387 respirator standards described earlier as being repre-
sentative of higher boiling, typically physisorbed, chemicals. No
studies have been identified which specifically examine the use
of MOFs to remove cyclohexane from a contaminated airstream.
However, the cyclohexene adsorption isotherms measured at
25 °C of HKUST-1, in comparison with a foam material con-
taining HKUST-1, zeolite ZSM-5 (ZSM = Zeolite Socony Mobil)
are given by Saini and Pires. A cyclohexene saturation capacity
of about 4 mmol g−1 was found for the pure MOF compound,
very similar to the value for n-hexane. A saturation value of
around 2.5 mmol g−1 was found for the composite material.
The saturation is observed at p/p0 = 0.2, equivalent to a par-
tial pressure of 2580 Pa. The isotherms show a strong slope in
Figure 6. Effects of relative humidity on the benzene breakthrough curves
the low pressure region, so high capacities can be assumed for in the fixed bed filled with the HKUST-1 at 308 K (benzene concentration:
much lower pressures, but no exact data can be extracted from 0.210 mmol mL−1, 16.38 mg L−1). Reproduced with permission.[108] Copy-
the published measurements.[107] right 2015, Elsevier B. V.
4.2.3. Toluene toluene value. The isotherms indicate a slight preference for
p-xylene over o-xylene, and a stronger preference for both over
A comparison of the toluene adsorption isotherms of two m-xylene at p/p0 = 0.2.
MOFs, HKUST-1 and MIL-101, is given by Xu et al.[109] MIL- Breakthrough curves of equimolar mixtures of the three
101 has two types of mesoporous cages, 34 and 29 Å in diam- xylenes and ethylbenzene in helium carrier gas at UiO-66 are
eter with 12 and 16 Å × 14.5 Å windows.[110] The pore system given from Bárcia et al.[114] Table 4 shows the structures and
of HKUST-1 shows a window size of 9 Å and a cage size of molecular data of the aromatic compounds addressed in this
10.8 Å. In addition, there are eight small pockets of 5.3 Å publication.
around each cage.[111] The pore volumes of samples used for They used total hydrocarbon pressures of 1 kPa
experiments are given to be 1.85 cm³ g−1 for MIL-101, and (10 000 ppm) and 10 kPa at 398 and 423 K. No information
0.46 cm³ g−1 for HKUST-1. The isotherms were measured at about residual concentrations before breakthrough can be
298 K. HKUST-1 outperforms MIL-101 at p/p0 < 0.1 (376 Pa), extracted from the given data, but they seem to be very low.
because of stronger interactions in the smaller pores. Capacity A total capacity of 15.2 wt% at 1 kPa and 398 K was observed.
values of about 6 mmol g−1, 553 mg g−1 (HKUST-1), and O-xylene is enriched in the MOF pores from an initial value
2 mmol g−1, 184 mg g−1 (MIL-101) are visible from the given of 25–35%. The authors discuss the influence of kinetic diam-
isotherms at p/p0 = 0.03 (113 Pa). The isotherm of HKUST-1 eters and van der Waals volumes of the adsorbed molecules
is very close to saturation at this pressure, while MIL-101 gives in comparison to the pore diameter. Schematic visualization
a saturation value of 14 mmol g−1 (1290 mg g−1) at p/p0 > 0.2, of cavities and windows of the UiO-66 structure is shown in
concluding that MIL-101 outperforms HKUST-1 at higher p/ Figure 7. A main finding reported is the molecule with larger
p0. This article shows that no recommendation for a best suit- kinetic diameter and lower van der Waals volume (o-xylene)
able MOF can be given for toluene adsorption in general, this is the most strongly adsorbed. The authors explain this effect
decision has to take into account the relevant concentration with different rotational freedoms of the molecules in the
values. small cavities of UiO-66.
Qin et al. measured room-temperature toluene adsorption A breathing MOF, called “DynaMOF-100”, was specially
isotherms for MIL-101 loaded with different amounts of PdCl2. designed for the adsorption of aromatics by Mukherjee et al.[115]
At p/p0 = 0.06, they measured a capacity enhancement of 450% It is built from Zn4O cores, known from the IRMOF family, and
for 3 wt% PdCl2/MIL-101 over that of unmodified MIL-101, very a specially synthesized linker containing two flexible oxygen
close to that of HKUST-1, and remains high total capacity at bridges. This compound is not porous in its initial state and
higher relative pressure. This work shows the high level of tun- shows a strong swelling in volume by the adsorption of styrene
ability of the adsorption properties by preloaded MOF pores.[112] or p-xylene. Ethyl benzene and the other xylenes are not adsorbed
in appreciable amount. Even though industrial separation of aro-
matics is the focus of the study, one can extract some benefits for
4.2.4. Other Aromatic Hydrocarbons trace gas separation from the published data. DynaMOF-100 is
able to adsorb 3.84 mmol g−1 (400 mg g−1) of styrene, which is a
The adsorption isotherms for the three xylene isomers (ortho-, very problematic pollutant off-gassing from the plastics and the
meta-, and para-) on MIL-101 are given by Trens et al.[113] insulation materials. There is a broad hysteresis in the isotherms
Although the main focus of this paper is chromatographic at 298 K, that indicates a strongly hindered desorption of the sty-
separation, not trace gas filtration, one can infer a saturation rene entrapped inside the pores. Selective pore opening in the
capacity of about 1200 mg g−1 at room temperature, which MOFs could therefore be used in ventilation systems to remove
is nearly the same for the three xylenes and very close to the styrene from indoor air, although selectivity over water and CO2
also has to be considered for this application.
Table 4. Structures and molecular data of the aromatic compounds
addressed in the publication of Bárcia et al.[114]
C 8 aromatic Structure Kinetic diameter van der Waals volume × 103

compound
p-xylene 0.67 nm 120.13 nm³
o-xylene 0.74 nm 119.91 nm³
m-xylene 0.71 nm 120.04 nm³
ethylbenzene 0.67 nm 120.20 nm³

Figure 7. Octahedral (left) and tetrahedral (right) cavities in UiO-66.
Zirconium polyhedral: purple, carbon atoms: grey. The free volume of the
cavities are presented in red (octahedral) and yellow (tetrahedral).
4.2.5. Halogenated and Noncyclic Hydrocarbons
The adsorption of the C5–C8 alkanes on MIL-101 and a com-

posite material containing 5% graphite oxide and 95% MIL-101
is addressed by Sun et al.[116] The isotherms at 298 K are reported
with resolved low pressure regions for the composite mate-
rial. They found saturation capacities between 10.8 mmol g−1
(779 mg g−1,n-pentane) and 7.2 mmol g−1 (822 mg g−1, n-octane)
for pure MIL-101, and 13.4 mmol g−1 (967 mg g−1, n-pentane) and
9.3 mmol g−1 (1062 mg g−1, n-octane) for the composite mate-
rial. These values are compared with capacities of the common
coal and silica materials, e.g., CMK-3 carbon with a n-pentane
capacity of 8.6 mmol g−1 (620 mg g−1),[117] BAX950 with a
n-octane capacity of 5.2 mmol g−1 (594 g g−1),[118] or MCM-48
with a n-pentane capacity of 8.2 mmol g−1 (591 mg g−1).[117]
The adsorption capacities for the different alkanes in the
composite material in the low pressure region are more distinct
from each other. Lowest resolved pressure is p/p0 = 0.02, which
means 32.4 Pa (324 ppm) in the case of n-octane, but 1360 Pa Figure 8. Single-crystal X-ray structures of ZIF-8 (left) and ZIF-4 (right).
The net is shown as a stick diagram below. The largest cage in each ZIF
(13 600 ppm) in the case of n-pentane. The capacities at is shown with ZnN4 tetrahedra in blue. H atoms are omitted for clarity.
p/p0 = 0.02 were found to be 6 mmol g−1 (685 mg g−1) for Reproduced with permission.[120] Copyright 2006, National Academy of
n-octane, but only 2 mmol g−1 (144 mg g−1) in the case of n-pen- Sciences U.S.A.
tane. This result shows once again, how well the defined pore
sizes make the MOFs promising materials for the adsorption as the linker compound. In contrast to ZIF-8, ZIF-4 has a hypo-
of the molecules in a relatively small size range. The better the thetical zeolite topology, not found in the natural or synthetic
molecule fits to the pore, the stronger are the interaction forces zeolites. The cage diameter is 4.9 Å, significantly smaller than
between the molecule and the pore walls. This lowers the equi- for ZIF-8. The aperture diameter is 2.0 Å (Figure 8). Both com-
librium pressure above the adsorbate. If there are unique sized pounds were tested for olefin/paraffin separation, with the
pores barely large enough, a larger molecule can be adsorbed adsorption isotherms and breakthrough curves being published.
much better than a smaller one at low pressures when equilib- Böhme et al. measured 293 K adsorption isotherms for ethane,
rium conditions are discussed. On the other hand, the adsorp- ethene, propane, and propene, and also breakthrough curves of
tion has to be faster for the smaller molecule. ethane/ethene and propane/propene equimolar mixtures on
Bárcia et al. measured the breakthrough curves for the ZIF-8 in comparison to two different MOF-74 homologues with
hexane isomers on UiO-66, in addition to the xylenes described magnesium or cobalt as framework metal, respectively.[121] The
earlier.[114] For measurements, mixtures of n-hexane, 3-meth- latter has an 11 Å wide channel structure and shows a steep slope
ylpentane, 2,3-dimethylbutane, and 2,2-dimethylbutane, equal in the hydrocarbon isotherms in the low pressure region. How-
amounts in helium carrier gas were used. Measurements ever, it must be considered that all the MOF-74 homologues are
on two different test concentrations (0.6 and 6.3 kPa total), extremely hydrophilic MOFs, due to the hydrophilic nature of the
and four different temperatures (343, 373, 423, 473 K) were linker compound (2,5-dihydroxyterephthalate) and the presence
examined. The total capacity for the mixed hexanes at 0.6 kPa of open metal sites. As an example, the pores of MOF-74(Ni) are
and 343 K is described as 9.35 wt%, not far from the value filled with water to an amount of 81% at a relative humidity of
found at a total hydrocarbon pressure of 6.3 kPa (10.89%). 5% and 298 K, so that an enhancement in hydrocarbon trace gas
With increasing temperature, the capacity at 0.6 kPa strongly filtration at ambient humidity for the MOF-74 series seems to be
decreases to 1.78% at 473 K. For hexane isomers, it was very unlikely.[122] The adsorption isotherms for propane and pro-
found that the amount adsorbed increases with the degree of pene measured on ZIF-8 are very similar to each other and show
branching, with 2,2-dimethylbutane and 2,3-dimethylbutane a moderate slope in the beginning, but a high total capacity of
being the more retained molecules. However, the most critical around 4.5 mmol g−1 (≈ 200 mg g−1). Ethane and ethene capaci-
point for air filtration, the capacity loss caused by the coadsorp- ties were found to be much lower. However, Böhme et al. found
tion of the water molecules, is not addressed in this paper. a very good separation effect for olefin/paraffin mixtures with
The so-called ZIF family includes some of the most hydro- paraffin preference (separation factors α = q(ethene)/q(ethane)
phobic MOFs, ideally suited for the adsorption of the hydrocarbons = 0.48 and α = q(propene)/q(propane) = 0.7), implying different
and other hydrophobic molecules from the moist atmospheres. adsorption kinetics for the olefins and paraffins.[121]
ZIF-8 is a framework of tetrahedral Zn2+ ions and 2-methylimi- However, from the perspective of trace gas adsorption, the
dazolate linkers crystallizing in the same topology as the zeolite hydrocarbon capacities are too low in the region of very low
sodalite. The diameter of the zeolite type cages is 11.6 Å, but the pressures. The same group published nearly the same experi-
apertures between the cages is only 3.4 Å. ZIF-8 shows no signifi- ments which were performed on ZIF-4.[123] In this case, due to
cant water adsorption at relative humidity below 90%.[119] the smaller pores, the propane and propene isotherms show a
ZIF-4 (Zn(C3N2H3)2) has a similar composition to ZIF-8, but very steep slope in the low pressure region, indicating the usa-
with nonsubstituted imidazole instead of 2-methylimidazolate bility of ZIF-4 for small hydrocarbons in trace amounts. The
total capacities are approximately reduced by half compared in industrial surroundings, where 1,3-butadiene is used as a
with ZIF-8. It may be reasonable to assume, that the apertures monomer. The selectivity could prevent the filter from satura-
of ZIF-4 can be passed by these molecules in their stretched tion with other, less toxic components. However, as seen in
state. The kinetic diameters of propane (4.3 Å), and propene Figure 9 effective adsorption takes place at pressures far away
(4.5 Å) barely fit within the cage diameter of ZIF-4, so that from trace concentrations.
much larger molecules cannot be adsorbed. For comparison, Tuning the adsorption of chlorinated hydrocarbons by the
n-pentane adsorption on ZIF-8 at 308 K shows a much steeper addition of functional groups of the MOF linker is addressed
type I isotherm than for propane or propene.[124] in the publication of Tian et al.[126] They compared the adsorp-
The adsorption of the C4 hydrocarbons 1,3-butadiene, tion behavior for dichloromethane (DCM) and trichloromethane
trans-2-butene, cis-2-butene, n-butane, 1-butene, iso-butene (TCM) on MOF-5 and IRMOF-3. The latter has the same cubic
compared with iso-butane is addressed by a work of Kishida microporous structure as MOF-5 but 7.8 Å in pore diameter,
et al.[125] A MOF compound named SD-65, [Zn-(NO2ip) and NH2 functionalities on its terephthalate linkers. Both the
(dpe)]n, (NO2ip = 5-nitroisophthalate, dpe = 1,2-di(4-pyridyl) compounds are regarded as model MOFs. Due to their water
ethylene) is compared to NaX zeolite, ZIF-8, MIL-53(Al), sensitivity they are not useful for applications at ambient condi-
[Zn2(fumarate)2(4,4′-bpy)] (bpy = bipyridine) and [Ca-(squarate) tions. They found DCM adsorption capacities of 8.49 mmol g−1
(H2O)]. While NaX, ZIF-8, and MIL-53(Al) adsorb not only and TCM adsorption capacities of 6.14 mmol g−1 for MOF-5.
1,3-butadiene but also n-butane and 1-butene with type-I pro- These capacities are compared with those of the activated carbon
files at 25 °C, flexible [Zn2(fumarate)2(4,4′- bpy)] shows a strong (1.88 mmol g−1 for DCM[127] and 4.8 mmol g−1 for TCM),[128] dea-
preference for 1,3-butadiene and 1-butene. [Ca(squarate)(H2O)] luminated faujasite Y (3.18 mmol g−1) for DCM,[129] and Na-Y5.5
showed adsorption profiles for trans-2-butene and 1,3-buta- zeolite (3 mmol g−1) for TCM.[130] In the case of IRMOF-3, these
diene well above those of the other five C4 gases. Only SD-65 values were improved up to 24.5% to 10.57 mmol g−1 (DCM) and
has a selectivity for 1,3-butadiene alone (Figure 9). 27.4% to 7.82 mmol g−1 (TCM). Only the DCM isotherms on
In the case of 1,3-butadiene, such a high selectivity is very IRMOF-3 show a slope sharp enough for trace gas adsorption.
advantageous because of its toxicity and carcinogenic character, The work of Britt et al., discussed earlier in relation to ben-
hence the WHO was not able to give a guideline value for this zene adsorption, also included breakthrough curves for DCM.[10]
compound.[17] One application may be seen in a selective filter They used a test concentration of 380 ppm DCM in N2 at 25 °C
and a flow rate of 25 mL min−1. The highest dynamic adsorp-
tion capacity of 0.055 g g−1 was found for HKUST-1, 114% of
the value measured for BPL carbon followed by MOF-74(Ni)
with 0.032 g g−1. Both the MOFs possess open metal sites,
which interact with the free electron pairs of the chlorine atoms.
Figure 10 shows breakthrough curves for the different MOFs
for benzene, dichloromethane, tetrahydrothiophene, and eth-
ylene oxide.[10] The results of this work of greatest relevance to
the topic of this review are summarized in Table 5.
As a conclusion, the unique pore shape and size, the pos-
sibility of functionalization and of having structural flexibility,
make MOFs well suited for adsorbing one single component or
a certain class of compounds. For the filtration of a nonspecified
hazardous gas mixture, a mixture of MOFs might be required.
5. Trace Gas Enrichment and Sensing

MOFs can significantly enhance the sensitivity of sensors in regard
to hazardous trace gases and act as trace gas sensors themselves.
Often the sensitivity of sensors is insufficient to detect trace
gases and vapors in real time and, therefore, preconcentrators
are essential for detecting the toxic substances. The MOFs as
thin films deposited onto a platform are an effective way to use
them as a concentrator for low concentration analytes, and also
known to provide the selectivity for analyte species. Typically a
mixture of many molecules including very low concentrations
of analytes is collected and trapped using special materials.
The trapping material is then heated to desorb the trapped spe-
Figure 9. a) Adsorption isotherms of SD-65 for 1,3-butadiene (pink open
cies. The mechanism of trapping is based on the adsorption
circles show the desorption isotherm), trans-2-butene (green), cis-2-bu-
tene (blue), n-butane (black), 1-butene (brown), iso-butene (purple), and phenomena on large surface area materials. Recent advances
iso-butene (gray) at 25 °C. b) Enlarged graph from 0 to 3 mL g−1 of amount in microfabrication have allowed the development of miniature
adsorbed. Reproduced with permission.[125] Copyright 2016, Wiley-VCH. preconcentrators that can be heated rapidly because of their low
Figure 10. A–D) Breakthrough curves of vapors tetrahydrothiophene (A), benzene (B), dichloromethane (C), and ethylene oxide (D) in the benchmark
MOFs. THT, tetrahydrothiophene; EtO, ethylene oxide. Reproduced with permission.[10] Copyright 2008, National Academy of Sciences U.S.A.
thermal mass. The microfabricated preconcentrators are coated safety in any scenario where the toxic gases can arise. Many gas
with high affinity materials, e.g., MOFs. detectors are based on sensing a change in resistivity or other
Explosives and toxic gases do play an important role in the nonselective material properties, often leading to low sensitivity
modern world. Sensing of concentrations in the lower ppm and selectivity.[131] For gas monitoring, a gas preconcentrator
and even ppb range presents significant challenges for sensor is often crucial for low-concentration gas analytes. By using
devices in regard to sensitivity, selectivity, and response time. preconcentrators, existing detection limits associated with the
As it is already known, the MOFs show great potential for commercialized gas sensors can be overcome. Typically porous
detecting a wide variety of substances in liquid and vapor phase. materials are used as preconcentration media, bringing the
detection limit down to the desired level. Porous polymers
like TenaxTA and activated carbons are very well known to be
5.1. Enrichment used for gas enrichment, e.g., in detection tubes followed by
TD and detection by GC or GC/MS. TD-GC or TD-GC/MS is
Most of the defined concentration limits of the toxic gases and among others a standard method for detection of the VOCs in
vapors are very low—down to the ppb region. Therefore, very ambient air in the TO-17 method of the United States Environ-
fast and sensitive detection technology is necessary to ensure mental Protection Agency (U.S. EPA).[132] Porous polymers and
Table 5. Dynamic adsorption capacities of the benchmark MOFs for gaseous contaminants measured in grams of gas per gram of adsorbent.[10]
Copyright 2008, National Academy of Sciences U.S.A.
Gas MOF-5 IRMOF-3 MOF-74 MOF-177 HKUST-1 IRMOF-62 BPL carbon Improvement
factora)
Sulfur dioxide 0.001 0.006 0.194b) <0.001 0.032 <0.001 0.033 5.88
Ammonia 0.006 0.105b) 0.093 0.042 0.087 0.023 0.001 105
Chlorine c) 0.335b) c)
<0.001 0.036 0.092 0.190 1.76
Tetrahydrothiophene 0.001 0.007 0.090 <0.001 0.351b) 0.084 0.123 2.85
Benzene 0.002 0.056 0.096 0.001 0.176b) 0.109 0.155 1.14
Dichloromethane <0.001 0.001 0.032 <0.001 0.055b) 0.019 0.053 1.04
Ethylene oxide 0.001 0.002 0.110 <0.001 0.095b) 0.011 0.010 9.50
a)Expressed as the ratio of dynamic adsorption capacity of the best performing MOF (b)) to that of BPL carbon; b)Best-performing MOFs; c)Experiments were not performed
because of corrosion of the apparatus by chlorine.
activated carbons perform well for most of the nonpolar gases. conditions for formaldehyde analysis using MOF-5 (-25 °C for
When it comes to polar analytes or very low concentrations, adsorption and 100 °C for desorption), the formaldehyde con-
most of the porous polymers and activated carbons do not centrations determined by analysis of three different sample
perform as well as required due to their nonpolar nature. volumes averaged 9.67 ppb, with high reproducibility. Formal-
Although the potential of using MOFs as preconcentrators dehyde concentrations obtained using TD-GC/MS measure-
seems to be very high, only a few articles that focus on that topic ments with MOF-5 were very similar to those determined using
have been published in recent years. In regard to respiratory the 2,4-dinitrophenylhydrazine cartridge-high-performance
protection, indoor and cabin air MOFs have been evaluated for liquid chromatography-UV system[134] which is commonly used
organic phosphonates (e.g., DMMP) and VOC enrichment (e.g., to track formaldehyde but the sampling procedure for TD- GC/
benzene, toluene, ethylbenzene, xylene, and formaldehyde). MS measurements with MOF-5 is much simpler.
As already mentioned formaldehyde is one of the most crit- For the enrichment of toluene, UiO-66 was deposited elec-
ical toxic gases that need to be controlled for indoor living. The trochemically as a film using zirconium foil as the metal
limit value of formaldehyde in air is in the low ppb region (see source.[135] This method enabled the straightforward integra-
Table 1 and Table 2). Therefore, the detection sensitivity of for- tion of UiO-66 as a sorbent film in a miniaturized sorbent trap
maldehyde sensors needs to be exceptionally high. In regard for online analytical sampling and concentration of toluene.
to preconcentration of formaldehyde, the use of MOF-5 as a The thin film was tested with a toluene gas concentration of
sorbent for infield sampling before thermal desorption GC/MS 200 ppm. The toluene enrichment in the outlet stream reached
determination (Figure 11) was described in 2010 by Gu et al.[132] a maximum concentration of 3.7 times the inlet concentration
This was indeed the first publication that describes the anal- (740 ppm). Reproducibility tests showed consistent device per-
ysis of real formaldehyde samples using MOFs. The authors formance over a large number of runs.
compared MOF-5 to reference materials such as TenaxTA Two metal–organic frameworks, HKUST-1 and MIL-53,
and graphitized carbon black. MOF-5 gave a 53 and 73 times have been characterized for their suitability as gas precon-
higher concentration effect than the two reference materials centration materials for benzene and toluene. By depos-
and comparable performance with those on molecular sieve iting the MOF material onto a micro hotplate integrated in a
13X and Carbosieve 1000. They even tested the cycling stability package together with a gas sensor, an integrated gas sensor
(200 cycles) and did not observe any significant loss of collec- microsystem was realized. In a dynamic adsorption–desorption
tion efficiency. The concentration of formaldehyde in the air process benzene preconcentration factors using the two
samples ranged from 12 to 48 µg m−3 and the recovery of for- MOFs could be determined, depending on the initial concen-
maldehyde from 93 to 107%. The effect of relative humidity tration of benzene. Test measurements were performed using
on the adsorption efficiency of MOF-5 for formaldehyde was benzene at concentrations of 10–1000 ppb. Both MOFs showed
additionally examined. In the presence of humidity the per- a higher preconcentration effect compared to TenaxTA. Even
formance for formaldehyde adsorption did not diminish sig- though benzene and toluene have fairly similar affinities to
nificantly as relative humidity increased up to 45%. Even the the MOF the preconcentration factor for benzene was more
exposure of MOF-5 to 100% humidity for 4 h did not show an than 50% higher compared to toluene. In case of 10 ppm ben-
impact on the effectiveness of MOF-5 sorbent. zene within the carrier gas, it was possible to obtain an enrich-
So far only Kim et al. investigated MOF-5 as an adsorbent ment factor of almost 700% using 60 min of adsorption and
for formaldehyde using TD-GC/MS measurements.[133] They 550% in case of 30 min. In case of 1 ppm, this value drops
developed a simple sampling technique and reliable analytical down to 460% for 60 min.[136]
procedure to quantify formaldehyde in ambient air samples. The first publications on the MOFs for preconcentration
Trace quantities of formaldehyde (e.g., 0.25 ng) were detected in micro GC systems were in 2007 by Ni et al.[137,138] They
when only 20 mL of air was collected. Using the optimal TD described the MOFs as novel adsorbents for preconcentration
of organic phosphonates. The MOF-5 was tested as an adsor-
bent for preconcentration using dimethyl methylphosphonate
(DMMP) and isopropylsulfonylchloride as a test case. DMMP
is a molecule that is commonly used as a simulant of nerve
agents. It has a polarity and volatility similar to that of sarin and
soman, but is much safer to use. Concentration factor gains of
more than 5000 are observed for DMMP with a 4 s sampling
time. If one instead uses TenaxTA in the trap, the gain is only
by a factor of two.
In 2015, MOF-5 was investigated for sampling of plant
volatile sulfides in Chinese chive and garlic sprout. Several
primary sulfur volatiles containing allyl methyl sulfide, dime-
thyl disulfide, diallyl sulfide, methyl allyl disulfide, and diallyl
disulfide were quantified. MOF-5 was immobilized on porous
copper foam support for enrichment. Results show that the
Figure 11. Schematic of sampling and desorption procedures on MOF-5 MOF-5@Cu-foam coating was thermally stable (up to 420 °C)
packed tube. Reproduced with permission.[132] Copyright 2010, American and robust enough for at least 200 cycles of adsorption and
Chemical Society. desorption. The authors propose an enhanced selectivity for
benzene series than for aliphatic esters, owing to the π−π solid–liquid sensing of various VOC selectively and reversibly
affinity between MOF-5 and phenyl ring in aromatic com- but also monitoring of acetonitrile vapor sensitively (Figure 12).
pounds. The extraction amounts of sulfides with the MOF-5 Recently, Eu(III)-functionalized ZnO@MOF heterostruc-
were 2.3−7.7 times of that with the reference PDMS material tures (Eu3+@ZUM) for the fabrication of a ppb-level sensing
(commercial poly(dimethylsiloxane)).[139] platform for volatile aldehyde gases in vehicles have been
described by Xu and Yan.[143] The heterostructure combines
the advantages of MOFs and semiconductor metal oxides to
5.2. Trace Gas Sensing improve the gas monitoring properties at room temperature.
The authors defined the MOF as a preconcentrator, the ZnO
The MOFs for trace and toxic gas sensing are based on as a reaction center, and the Eu3+ as a center of charge transfer
optical changes such as luminescence, mechanical sensors from the reaction centers into fluorescence sensing signals. For
(e.g., weight-detectable quartz crystal microbalance (QCM)) sensor testing, Eu3+@ZUM was integrated in a filter paper and
or changes in resistivity (e.g., in combination with semicon- exposed to the main volatile gases (benzene, toluene, xylene,
ducting materials). However, this review focusses less on the ethylbenzene, formaldehyde, butyl acetate, and cyclohexane,
various sensing methods than on the material selection for each 10 ppm) at 25 °C for 30 min followed by photolumines-
detection of different analytes in the trace gas range. cence measurements. The results are shown in Figure 13.
For this mixture of gases an exclusively significant reversible
change in photoluminescence was observed for formalde-
5.2.1. Volatile Organic Compounds hyde. The detection limit for formaldehyde was calculated
to be 42 ppb using an equation from Xu and Yan, 2017.[143]
VOCs like toluene, benzene, xylene, ethylbenzene, cyclohexane,
and formaldehyde are studied together in many publications.
Therefore, we will focus on VOCs in general and highlight some
more publications on formaldehyde detection using MOFs.
One of the first publications for trace gas VOC sensing using
MOFs was in 2011.[140] A floating gate field effect transistor
gas sensor based on work function readout was combined
with HKUST-1 as the sensor layer. They tested the response to
1 ppm hexanal, 1 ppm pentanal, and 5 ppm toluene at tempera-
tures from 25 to 100 °C. A distinct and reversible response was
observed during exposure to pentanal with increasing tempera-
ture, but not for hexanal and toluene. Polar inorganic gases like
NH3 and H2S (which will be reviewed in a lower section of this
part) showed strong changes in work function as well.
Luminescent-based materials can recognize various types
of target gases. In 2015 Hou et al. published the first results
on luminescent MOFs for cyclohexane detection.[141] The lan-
thanide based Tb-MOF {[Tb2(NO3)2(edc)(DMF)4]DMF H2O}n
(edc = 5,50-(ethane-1,2-diylbis-(oxy))diisophthalate) could iden-
tify cyclohexane and nitrobenzene with high sensitivity and
rapid regeneration. The luminescent response was investigated
after exposure to organic solvents in liquid phase for acetoni-
trile, acetone, acetylacetone, n-hexane, cyclohexane, 1,4-dioxane,
benzene, toluene, p-xylene, nitrobenzene, benzaldehyde, meth-
anal, ethanal, and propanal. For the Tb-MOF, cyclohexane sig-
nificantly enhanced the luminescence, whereas the remaining
solvents decreased the luminescence intensity indicating that
the MOF can be considered as a probe to detect cyclohexane
in a mixture of VOCs in liquid phase. Furthermore, tests using
cyclohexane vapor at 25 °C also showed a significant effect on
the luminescence intensity.
A pronounced guest responsive color change of fluorescence
emission of [(CuCN)3L(guest)x]n (L = 2,6-bis((3,5-dimethyl- Figure 12. a) Real-time monitoring of the solid-state emission spectra of
1H-pyrazol-4-yl)methyl)pyridine; x = 1 or 2) upon adsorption of the thin film sample of 2 in response to acetonitrile vapor. The inserted
various volatile organic solvent molecules in liquid phase has plot shows the subsequent sensing process upon adding one or two
drops of acetonitrile solvent, showing the decreasing of the 450 nm peak
been reported by Wang et al.[142] In addition to the pronounced
and the increasing of 530 nm peak. b) The linear relationship between
luminescence properties, the MOF material shows structural emission intensity and log(t/s) deduced from six sets (28 to 210 s, the
dynamics upon adsorption of various VOC, i.e., acetonitrile. This first three minutes) of the emission spectra. Reproduced with permis-
luminescent MOF material is capable of not only the qualitative sion.[142] Copyright 2013, Royal Society of Chemistry.
revealed clear groupings of the data by functional groups with

a high degree of confidence. These results establish conductive
MOFs as a distinct new category of chemiresistor materials.
A 2D Cu-based MOF, Cu(bdc)·xH2O, was investigated for
integration in capacitive sensing structures for the detection of
humidity and VOCs.[145] In this study, the MOF was grown as a
thin film on interdigitated electrodes. In addition to humidity,
acetone, ethanol, methanol, and toluene have been used as test
probes for the evaluation of the sensor element. The change of
capacitance of Cu(bdc)·xH2O has linear behavior for acetone,
ethanol, and methanol in the tested VOC concentration range
(up to about 17 000 ppm). Due to their similarity in chemical
nature and size, acetone, ethanol, and methanol show a similar
sensor response. As a result of π–π interaction with the benzene
rings of the ligand of the MOF thin film, the sensor is more
sensitive at low concentrations (125–500 ppm) for toluene.
Detection of VOCs using QCM and silicon-based microcan-
tilever sensors coated with the MOF thin films was described
by Yamagiwa et al.[146] QCM detect analytes by sensing small
changes in the frequency of a resonant vibration as a result of
weight changes on a nanogram level. Thin films of HKUST-1
and MOF-5 were grown onto gold electrodes of QCMs or
silicon microcantilevers. The HKUST-1 layer was tested for
toluene detection. The response increased linearly in the con-
centration range of 0–100 ppm and saturated above 100 ppm.
Figure 13. a) The photoluminescence emission spectra and b) intensi-
ties (I614 and I470) of Eu3+@ZUM test paper after exposure to various The lower detection limit was defined to be 1 ppm. To assess
pollutant gases in vehicles (lex ¼ 365 nm). The inset photos of (b) are the dependence on polarity and size of the analyte molecules,
the corresponding images under UV light irradiation at 365 nm and the the authors compared vapor response isotherms of QCM sen-
numbers are the I614/I470 values. CH-cyclohexane, Tol-toluene, BA-butyl sors modified with HKUST-1. Comparing the ethanol, acetone,
acetate, EB-ethylbenzene, OX-o-xylene, MX-m-xylene, PX-p-xylene, Ben- toluene, and n-octane vapor response isotherms, the more polar
benzene, FA-formaldehyde. Reproduced with permission.[143] Copyright
analytes (ethanol and acetone) respond in a higher analyte
2016, Royal Society of Chemistry.
uptake in the HKUST-1 layer. For alkanes and alkyl alcohols
no significant difference in the adsorption isotherm was reg-
The composite material was also tested for other aldehydes istered for analytes with identical chain length. The response
(acetaldehyde and acrylaldehyde). Again, as for the mixture sequence followed the molecular size of the VOCs: n-hexane,
with formaldehyde a pronounced emission due to the aldehyde n-hexanol, n-heptane, n-heptanol, n-octane, and n-octanol. With
adsorption was detected with detection limits of 58 ppb for increasing chain length of the analyte molecule, the adsorption
acetaldehyde and 66 ppb for acrylaldehyde. If a mixture of for- uptake decreases. In addition it was shown that the recognition
maldehyde, acetaldehyde, and acrylaldehyde is applied to the of the positional isomers of xylene compounds by the HKUST-1
sensor, all the concentrations of the mixed gases can produce layer can be differentiated. The MOF-5 was also investigated in
the fluorescence enhancement effect for the Eu3+ based emis- the same way as HKUST-1. Compared to HKUST-1, the selec-
sion with an enhanced effect larger than that achieved from tivity of MOF-5 layer for the VOCs was lower. The structural
a single gas. The Eu(III)-functionalized ZnO@MOF hetero- difference between HKUST-1 and MOF-5 affected the responsi-
structure has great potential for detecting various aldehydes in bility and selectivity of the VOC sensing. The authors explained
a VOC mixture. the difference by the larger pore and aperture sizes in MOF-5
Beyond luminescent MOFs, 2D MOFs show great poten- which induce a low molecular sieving effect for the selective
tial integrated in chemiresistive sensor devices. Campbell sorption of the VOCs.
et al. demonstrate that a sensor array constructed from three Surface-enhanced Raman scattering (SERS) has been inten-
structurally analogous (Cu3(HHTP)2, Cu3(HITP)2, Ni3(HITP)2, sively investigated by chemical detection. SERS operates at
HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene, HITP = ambient conditions, can be portable and is able to detect sub-
2,3,6,7,10,11-hexaiminotriphenylene), but chemically dis- stances down to the single molecule level. To enhance the
tinct, conductive 2D hexagonal MOFs can reliably distinguish adsorption and therefore the range of the molecules which are
between five categories of VOCs (aliphatic hydrocarbons, alco- assessable by SERS technology, Kreno et al. determined the
hols, ketones/ethers, aromatic hydrocarbons, and amines) influence of ZIF-8 films on Ag to detect a range of structurally
based on functional group.[144] The MOFs are based on triph- similar VOCs: Upon exposing the MOF thin layers to benzene,
enylene-derived ligands with square planar metal centers. The toluene, nitrobenzene, or 2,6-di-tert-butylpyridine, the MOF
MOFs are generally responsive to VOCs with polar character, film traps the vapors allowing the unique Raman spectrum of
while all three materials show no appreciable response to ali- each vapor to be recorded. These VOCs are not detectable by
phatic hydrocarbons. Statistical analysis of the sensing data SERS using nonfunctionalized surfaces.[147]
Formaldehyde sensors with high sensitivity and selectivity ZIF-8 was explored in regard to photoluminescent inten-
are particularly desirable. The acceptable indoor formaldehyde sity of the guest-free phase and loaded with formaldehyde.
concentration is set to 0.1 mg cm−3 (≈82 ppb). Over recent dec- Luminescence properties were evaluated in the concentration
ades, a variety of gas sensors based on semiconducting metal range of formaldehyde up to 20 ppm. The authors defined an
oxides has been developed to monitor formaldehyde. How- exposure time of 5 min using 20 ppm formaldehyde to get the
ever, such inorganic sensors often require a high temperature maximum changes in emission intensity by experiments. The
(200−400 °C) to achieve optimum measurements. Furthermore, photoluminescent emission intensities of ZIF-8 at 410 nm
they are limited by low surface areas, whereas the optimum gas were determined after exposure to various formaldehyde con-
sensing process is strongly dependent on the large surface area centrations (20, 15, 10, 5, 1 ppm, 500, 250, 100, and 0 ppb) to
that permits the sensing material to absorb more gas molecules evaluate the sensitivity of the ZIF-8-based sensing platform.
and then improve the response and therefore sensitivity.[148] The limit of detection for gaseous formaldehyde was calcu-
In 2014, Yu et al. published a Cu(I)-based MOF as a colori- lated to be 0.057 ppm which satisfies the requirements for
metric sensor for water and formaldehyde. The water loaded indoor danger threshold set by OSHA and the safe-exposure
Cu(I)-MOF showed a color change to orange, deep-orange, and standard set by the WHO. Regeneration tests have been car-
light brown in 1.6, 0.16, and 0.016 ppm formaldehyde vapors ried out under vacuum at 150 °C. The emission intensity of
(Figure 14). No obvious naked-eye detected color change was ZIF-8 was regenerated completely and emission intensity
observed in 1.6 ppb formaldehyde vapor. Besides the naked- at 410 nm maintained its original intensity even after sev-
eye detection, formaldehyde encapsulation was also detected by eral cycles of exposure to formaldehyde. Other pollutants,
pronounced changes in emission spectra. The emission inten- such as benzene, toluene, methanol, and ethanol (at 2 ppm
sities increase with increasing amount of adsorbed formalde- concentration) in combination with formaldehyde (2 ppm)
hyde in the Cu(I)-MOF samples. There is no influence on the showed just little or no interference with the photolumines-
structural properties of the Cu(I)-MOF in presence of water. cence intensity of ZIF-8 compared to the testing of ZIF-8 with
Therefore, it is a potential material for a portable formaldehyde single component formaldehyde. The authors conclude that
sensing device in ambient conditions. In addition the guest/ the enhancement of emission intensity is most likely due to
exchange processes are reversible and single-crystallinity of the the specific interaction of formaldehyde with the host frame-
Cu(I)-MOF is maintained during the sensing process.[149] work of ZIF-8.[152]
Another potential luminescent MOF for formaldehyde Another approach was to use ZIF-8 as a material to improve
detection was described by Yao et al.[150] They investigated the selectivity for formaldehyde detection in already established
the hydrogen bond between formaldehyde and [Zn(NH2bdc) detection systems.[153] ZnO was covered by ZIF-8 in a core–
(bix)]n (NH2bdc = 2-amino-1,4-benzenedicarboxylate and bix shell heterostructure. ZnO@ZIF-8 nanorods integrated in a
= 1,4-bis(imidazol-1-ylmethyl) benzene) using density func- sensor device exhibited distinct gas response for reducing gases
tional theory and time-dependent density functional theory. with different molecule sizes due to molecular sieving effects
[Zn(NH2bdc)(bix)]n shows luminescence at 426 nm. The of the ZIF-8 material whereas conductance and chemiresis-
strength of the luminescence would increase and the lumines- tive behavior is supported by ZnO. The working temperature
cence wavelength would be altered when the MOF interacts to operate the sensor experiments was chosen to be 300 °C
with a variety of small molecules.[151] From the computational in order to keep the good gas sensing property of ZnO and to
experiments, the authors claim the MOF to be possibly appli- avoid the breakdown of ZIF-8. The sensing performance of the
cable for detecting formaldehyde. composite material was even tested for 100 ppm formaldehyde
in dependence on humidity. The performance of the sensor
was reduced when relative humidity exceeded 80%. However,
in terms of the performance of the ZnO@ZIF-8 sensor in the
presence of different VOCs, such as formaldehyde, ethanol,
ammonia, acetone, toluene, and methanol, the selectivity for
formaldehyde is pronounced compared to the common ZnO
sensor material (Figure 15).
In 2014, Chen et al. published the potential use of ZIF-67
(Co(mim)2; mim = 2-methylimidazolate) for formaldehyde
detection due to changes in resistivity as is very well known
for semiconducting materials such as the already mentioned
ZnO. ZIF-67 is shown to be a promising formaldehyde gas
sensor at a low operating temperature (150 °C). To find the
optimum conditions, gas sensing measurements were per-
formed by exposing the obtained sensor to 100 ppm of
diverse gases (formaldehyde, methanol, acetone, ammonia,
and methane) at various operating temperatures. The sensor
response was evaluated as a function of operating tempera-
Figure 14. Photographs showing the color change of the bulk samples
of Cu(I)-MOF in formaldehyde vapor with different vapor concentrations. ture. The ZIF-67 sensor had the highest response to formal-
The single-crystal nature was kept during the color change process. Repro- dehyde. Remarkably, the response to ammonia and methane
duced with permission.[149] Copyright 2013, Royal Society of Chemistry. is very weak.[148]
Figure 15. a,b) Gas response transient curves and the selectivity of the ZnO@ZIF-8 nanorods sensor to 100 ppm of different VOCs at working tempera-
ture of 300 °C. c,d) Gas-sensing transient curves and the selectivity of the ZnO nanorods sensor to 100 ppm of different VOCs at 300 °C. Reproduced
with permission.[153] Copyright 2015, American Chemical Society.
5.2.2. Inorganic Hazardous Trace Gases
Ammonia is a colorless, volatile, and corrosive gas with a pun-

gent smell (odor threshold is 5 ppm). It is toxic and harmful to
human health. To protect people from excessive ammonia expo-
sure, NIOSH has stipulated that the immediately dangerous to
life or health (IDLH) concentration of ammonia is 300 ppm
based on acute inhalation toxicity data in humans.[154] OSHA
have set the limit for ammonia for an eight hours working day
to 50 ppm.[154] There is a need to ensure these safety issues by
using sensor devices.
In 2013, Shustova et al. reported remarkable high-tem-
perature ligand-based fluorescence MOFs, Zn2(TCPE)
(TCPE = tetrakis(4-carboxyphenyl)ethylene) and Mg(DHBDC)
(DHBDC = 2,5-dihydroxybenzene-1,4-dicarboxylate), working
as selective sensors for ammonia at 100 °C, although both
materials do not show ammonia selectivity at room tempera-
ture (Figure 16). Interaction of ammonia with Zn2(TCPE) and
Mg(DHBDC) causes fluorescence shifts and turn-on lumi-
nescence at elevated temperatures. The two MOFs preferen-
tially respond over a variety of potential interferences such as
water, methanol, and larger amines. The exposure of activated
Zn2(TCPE) to ammonia, triethylamine, ethylenediamine (en),
DEF, and water vapors at room temperature shifted its emis-
sion maximum by 0−23 nm. However, monitoring the effect
of these analytes at 100 °C showed that only ammonia expo-
sure led to a significant shift of the emission maximum from
487 to 511 nm. Unfortunately, ammonia binding also caused
an irreversible phase change in Zn2(TCPE) to an unidentified Figure 16. In situ normalized emission spectra (λex = 350 nm) of
crystalline form, which suggested that this material would not Zn2(TCPE) exposed to various analytes at room temperature and 100 °C.
be effective in a reversible sensing application.[155] Reproduced with permission.[155] Copyright 2013, American Chemical Society.
Sel et al. published in 2015 the use of trimesic acid (TMA) found to be 7% for one sample at 500 ppm ammonia. Although
based MOFs for ammonia detection. Changes in conductivity at the changes in resistance are not very large, the authors were
room temperature of the prepared TMA-M (M = Ba(II), Cd(II), able to show that the chips tested exhibit reversible sensing.
Pb(II), and Zn(II)) against ammonia gas were investigated and When the chips were purged with air, ammonia was removed.
a considerable response change was detected for all MOFs. Hao and Yan synthesized an intense luminescence MOF
Especially for the TMA-Zn MOF, a significant change in the material, Eu3+@Ga(OH)bpydc (bpydc = 2,2-bipyridine-5,5-
room temperature conductivity was determined.[156] dicarboxylate) by postfunctionalization.[160] The europium ions
In 2015, Campbell et al. demonstrated the usability of the were immobilized at the accessible 2,2-bipyridine sites on the
conductive 2D MOF Cu3(HITP)2 to fabricate chemiresistive linker molecule. Eu3+@Ga(OH)bpydc can detect ammonia
sensors with sub-ppm sensitivity to ammonia vapor at room selectively and sensitively among various indoor air pollutants.
temperature and with an applied potential of 100 mV. This The authors proposed the MOF as a rare example of a lumi-
work represents the first successful use of conductive MOFs in nescent sensor that can monitor pollutants in the environment
chemiresistive sensors. Device performance was maintained in and also detect their biological markers. Eu3+@Ga(OH)bpydc
air with up to 60% R.H. It was also found that devices fabri- was fabricated as a nanoscale MOF film by spin-coating and
cated from the isostructural MOF Ni3(HITP)2 did not display used to evaluate the sensing performance. As can be seen in
sensitivity to ammonia vapor under identical conditions, indi- Figure 18, the europium-doped MOF was tested for its ability to
cating the potential for tuning the sensors response based on sense indoor air pollutants, including formaldehyde, benzene,
the MOF chemical structure.[157] ammonia, and TVOCs (benzene, toluene, o-xylene, ethylben-
Another chemiresistive sensing device based on 2D MOF zene, styrene, butyl acetate, n-undecane). Surprisingly most
materials (already mentioned for VOC detection) has been organic vapors had a negligible effect on the luminescence of
described in a study published in 2016.[158] The development the MOF film, except in the case of ammonia, which induced
of a rapid and straightforward method for
the preparation of chemiresistive sensors
based on conductive MOFs, Cu3HHTP2
and Ni3HHTP2, self-assembled on shrink-
able polymeric films equipped with minia-
turized graphitic electrodes was described.
The two MOFs showed different changes
in resistivity, depending on the analyte. The
results are shown in Figure 17. For ammonia
the resistivity of the Cu-containing MOF
increased whereas no change in resistivity
for the Ni-containing MOF was observed.
By comparison a significant increase in
resistivity was observed upon exposure to
H2S with Ni3HHTP2. Exposure to NO pro-
voked a consistent decrease in resistivity of
devices for both MOFs. In regard to these
results, the authors described the sensors as
being capable of detecting and differentiating
ammonia, NO, and H2S at ppm concentra-
tions (up to 80 ppm).
Travlou et al. determined the capability
of HKUST-1 in combination with graphene
oxide (GO) as chemiresistive ammonia sen-
sors at dry conditions.[159] Taking into account
the good performance of MOF–GO/MOF-
GOU (GOU = urea graphene oxide) compos-
ites as ammonia adsorbents, they examined
the sensing response of these materials as
a function of ammonia concentration. The
microchips were initially exposed to 500 ppm
ammonia. Subsequently, the extent of revers-
ible sensing was explored. For this purpose
the chips were exposed to ammonia concen-
Figure 17. A) Concentration-dependent sensing response (left to right, NH3, NO, and H2S)
trations, varying from 100 to 500 ppm. For all
for Cu3HHTP2 and Ni3HTTP2 in orange and blue, respectively. Error bars represent standard
samples, the normalized resistance increased deviation from average exposures (3 × 80 ppm, 9 devices). B) Representative sensing traces
with increasing ammonia concentration. The (3 × 80 ppm) for Cu3HHTP2 and C) representative traces (3 × 80 ppm) for Ni3HTTP2. Repro-
highest change of normalized resistance was duced with permission.[158] Copyright 2016, American Chemical Society.
Figure 18. a) Photoluminescence spectra of Eu3+@Ga(OH)bpydc film after exposure to various indoor gas pollutants for 1 h; b) relative emission
intensities at 614 nm (λex = 338 nm). The inset shows the corresponding photographs under 365 nm UV irradiation. EB-ethylbenzene, BA-butyl acetate,
Ben-benzene, OX-o-xylene, Tol-toluene, Sty-styrene, Und-n-undecane. Reproduced with permission.[160] Copyright 2015, Royal Society of Chemistry.
a remarkable reduction (76%) in the luminescence intensity metal–based metal–organic framework.[163] The MOF-based
of Eu3+ at 614 nm. The intensive change in luminescence due sensor was made by in situ growth of a fumarate-based MOF
to ammonia could be distinguished easily by the naked eye. thin film on a capacitive interdigitated electrode. The sensor
To investigate the ammonia detection limit of the sensor, the showed remarkable detection sensitivity for H2S at concentra-
MOF film was exposed to different ammonia concentrations tions down to 100 ppb, with the lower detection limit around
at room temperature. The changes in the luminescence inten- 5 ppb. The fumarate-based MOF sensor exhibits highly desir-
sity at 614 nm were recorded. The detection limit of the sensor able detection selectivity toward H2S versus CH4, NO2, H2, and
was examined to be 2.4 ppm. The quenching efficiency gradu- C7H8 as well as an outstanding H2S sensing stability as com-
ally increased with NH3 concentration from 10 to 500 ppm. pared to other reported MOFs.
Eu3+@Ga(OH)bpydc showed high selectivity (76% reduction of A variety of MOFs (MIL-100(Fe), MIL-101(Cr),
luminescence), high sensitivity (detection limit, 2.4 ppm), fast Zn3(BTC)2·12H2O and ZIF-8) have been investigated as H2S
response (≈30 s), and quick regeneration by ambient air. cataluminescence (CTL) sensors at 250 °C, a flow rate of
A very recent publication focuses on the field-effect chem- 200 mL min−1 and H2S concentrations ranging from 6.16 to
ical sensors using UiO-66-NH2 for nerve agent (alkyl phospho- 15.39 ppm.[165] The CTL experiments with MIL-100(Fe) at a
nate, DMMP) detection.[161] The [Zr6O4(OH)4]12+ cluster of the H2S concentration of 15.39 ppm gave inconsistent results, sug-
UiO-66 type materials has been of specific interest because gesting the destruction of the MIL-100(Fe) material. The same
of its remarkably high activity toward phosphate ester hydrol- was observed for the MIL-101(Cr) material in a CTL experi-
ysis.[162] Signal transduction was achieved by monitoring the ment. Zn3(BTC)2·12H2O and ZIF-8 displayed good sensitivity
work function shift of UiO-66-NH2-coated electrodes upon and stability for H2S. The detection limit of Zn3(BTC)2·12H2O
exposure to ppb-level (down to 3 ppb) concentrations of the was determined to be 4.4 ppm and for ZIF-8 3.0 ppm (con-
target simulant. The extrapolated limit of detection for DMMP cluded from a calibration curve). In addition the authors deter-
was found to be 0.3 ± 0.1 ppb and the observed response mined response and recovery time as well as reproducibility
time was 1.9 ± 1.3 min. Even in combination with humidity test for Zn3(BTC)2·12H2O and ZIF-8. The response time to
(50% R.H.), a high sensitivity for DMMP was observed due to H2S for Zn3(BTC)2·12H2O was determined to be less than 0.3 s
much higher affinity of the adsorption sites in UiO-66-NH2 for and a recovery time less than 1.0 s. For ZIF-8, the response
DMMP than for water. time was even less than 0.1 s and the recovery time lower than
Several studies undertaken by occupational safety and 0.5 s. The authors also investigated the responses of methanol,
health institutions have indicated that exposure to H2S ethanol, propanol, butanol, iso-butanol, acetone, formaldehyde,
(above 2–5 ppm) has health effects on the human respira- toluene, and chloroform at a carrier gas rate of 200 mL min−1
tory system, which could then lead to neurological sequelae and temperature of 250 °C on ZIF-8 and Zn3(BTC)2·12H2O
to exposure above 100 ppm. Furthermore, exposure to above with a concentration of 119.70 ppm. With this the authors
1000–2000 ppm leads to nearly instant death.[163] H2S generally showed the high selectivity of ZIF-8 and Zn3(BTC)2·12H2O for
known for its toxicity and characteristic smell of rotten eggs, H2S at the given concentration of analytes.
has an odor threshold of 0.01–1.5 ppm. H2S can be rapidly The detection of NO2 is of crucial importance as well. NO2 is
absorbed by the lungs once exposed by inhalation. NIOSH has a common atmospheric pollutant produced during combustion
stipulated that the IDLH of H2S is 100 ppm, while OSHA has reactions, with a toxic effect on the respiratory system at con-
set the limit for H2S for an eight hours working day to 10 ppm. centrations of 1 ppm (NIOSH) and below. The IDLH of NO2 is
Therefore, monitoring the concentration of H2S in the atmos- 20 ppm.[166]
phere is especially important.[164] Apart from the publication of Smith et al.,[158] one other
Yassine et al. fabricated an advanced sensor for the detec- MOF is described in the literature for detection of nitrous
tion of H2S at room temperature, using thin films of rare-earth gases. Nickerl et al. reported about “tetrazine functionalized
zirconium MOF as an optical sensor for oxidizing gases.” Zr6 region). The MOF materials have most often been reported for
O4(OH)4(bdc)5.1(dhtz)0.9 was generated by postsynthetic ligand the detection of small explosive amounts.[169] The most estab-
exchange. The original UiO-66 structure was modified by lished way for detection relies on changes in the fluorescence
dihydro-1,2,4,5-tetrazine-3,6-dicarboxylate (dhtz) in a ratio of spectra of the sensor material.[170–172] The explosive compounds
bdc:dhtz of 5.1:0.9. Dihydro-1,2,4,5-tetrazine (yellow) unit is that lead to changes in luminescence properties are mainly aro-
easy to oxidize to 1,2,4,5-tetrazine (pink). The color change by matic nitro compounds. Unfortunately not only aromatic explo-
oxidation (see Figure 19) is used for sensing NO2.[167] sives of this group lead to changes in fluorescence properties
Just recently, a conductive porous composite material made of MOFs but also other volatile organic compounds with sim-
from poly(3,4-ethylenedioxythiophene) (PEDOT) and MIL- ilar structures such as nonexplosive nitrobenzene can interact
101(Cr) has been described and proposed to act as a chemiresis- in the same manner.[169,173,174] One of the first examples of an
tive sensor for the detection of NO2 with increased accessibility explosive detecting MOF was given by Li and co-workers for the
and sensitivity compared to PEDOT itself.[168] PEDOT is shown detection of 2,4-dinitrotoluene (DNT) and 2,3-dimethyl-2,3-di
to exhibit show changes in conductivity in contact with oxi- nitrobutane (DMNB) with [Zn2(bpdc)2(bpee)] (bpdc = 4,4′-biphe-
dizing agents. To find the best performing composite for NO2 nyldicarboxyliate, bpee = 1,2-bipyridylethene).[175] Both analytes
sensing, various amounts of PEDOT infiltrated in MIL-101(Cr) induce a quenching of the MOF fluorescence combined with
were tested. This composite with 45 wt% PEDOT in MIL- a shift of the maximum to higher wavelengths with a very fast
101(Cr) showed the best compromise between high conduc- response of the MOF at very low loadings in vapor phase (e.g.,
tivity and high accessibility for the gas molecules. The response 2.7 ppm DMNB).
time was reported to be below 30 s for low partial pressures The most challenging aspect is the specific detection of an
and remained below 150 s up to 20 ppm NO2. The conductivity explosive group or several specific substances.[176–181] In the
increase was found to be linear up to 10 ppm NO2. The min- field of MOFs, the presence several functional groups enhances
imum NO2 concentration measured was 200 ppb, with a sensor the specific detection of explosive analytes. In recent years, the
response of 0.9%. detection of single explosives or groups with specific motifs
has become possible. Systematically MOF networks are func-
tionalized with ligands, which offer stronger interactions
5.2.3. Explosives between the analyte and the network.[176,177,182,183] Specific
interactions of such a host–guest system lead to a higher con-
The detection of explosives can encompass two scales; first, tent of interacting analyte inside the pore system. In contrast
the detection of bulk materials, for which a large amount of to analytes without such behavior, the enrichment in a sensor
the substance is present, and second the detection of trace material delivers a faster sensor response at low concentra-
amounts, where only small amounts of the analyte are available. tions. In addition to experimental studies, the enrichment of
An example for the latter case is the explosives control at hands explosives with MOF systems could be explored by theoretical
or clothes by swabbing at the airport. Therefore, materials are calculations. Odbadrakh et al. used IRMOF-8 as model system
needed which are sensitive to very low concentrations (in ppm for the interaction with RDX and TATP.[184] Further studies
Figure 19. Reversible oxidation and reduction of the tetrazine unit in UiO-66 and the corresponding change in color. Reproduced with permission.[167]
Copyright 2014, Royal Society of Chemistry.
on IRMOF-series and RDX as analyte indicate the advantage observed. By “turn off” and “turn on” both groups of analytes
of amine functionalized ligands.[185] In contrast to IRMOF-1 could be discriminated. The behavior was explained by dif-
or IRMOF-10 (Zn4O(bpdc)3), IRMOF-3 and amine functional- ferent charge and energy transfer interactions between host
ized IRMOF-10 (IRMOF-10a and IRMOF-10b) show a higher (MOF with dye) and each group of analytes.
RDX loading during physisorption modeling, which indicates a By functionalization of UiO-66 with 2-aminoterephthalic
better preconcentration inside the pores. acid (UiO-66-NH2) instead of terephthalic acid, the detection of
For the detection of explosives, Cu-MOP (MOP = metal– nitroaromatic explosives with hydroxyl groups is possible.[182]
organic polyhedral) with an amine functionalized ligand H2 In particular, the detection of 2,4-DNP (2,4-dinitrophenol) was
(2-NH2-5-i-Pr-3,3′-3,3′-(1,3-phenylenebis(ethyne-2,1-diyl))diben- successful by quenching of the MOF fluorescence properties.
zoate) was used.[186] Li and co-workers studied the interaction Compounds like 2,4-DNT or TNT, without hydroxyl groups,
of a host system with different analytes such as TNT, DNT, show no effect. By interaction of host based amine groups
RDX, and HMX. The formed complexes were investigated by with hydroxyl groups of the explosive an enrichment of the
the utilization of different techniques (e.g., UV–vis, Fourier explosives inside the pore system was identified. Stable Zr-
transform-IR, electrospray ionization, and SERS). As a con- networks, combined with ligands carrying free amine groups
clusion the selective detection with a reversible behavior was were also successfully used for preconcentration and sensing
possible. The same group incorporated in later experiments of picric acid (TNP) in place of 2,4-DNP.[177] The enrichment of
successfully the dye (E)-4-(4-(dimethylamino)styryl)-1-meth- 2,4-DNP and TNP in the network based on hydrogen-bonding
ylpyridin-1-ium in bio-MOF-1[187] to detect different kinds of interactions between network amine groups and free hydroxyl
explosive analytes.[176] During the enrichment of the analyte groups on the explosive occurs as a consequence of higher con-
inside the pores of the host system an interaction between dye centrations in the network.[177,188] The enrichment of TNP does
and analyte was observed. As analytes both aromatic (TNP, not only depend on free amine groups. Other groups show
TNR (2,4,6-trinitrobenzene-1,3-diol), DNT, TNT) and aliphatic that the presence of azo-groups in the linker backbone,[189]
(linear and cyclic) (RDX, HMX, PETN, DMNB) explosives cyano- or tetrazol- side groups,[190] urea- side groups[191] as well
were tested. Figure 20 gives an overview about the structure of as urotropine-ligands[192] achieved the same effect. Preconcen-
various explosives for better understanding. In the case of aro- tration through specific interaction leads to a faster quenching
matic explosives, a “turn off” effect with a quenching behavior behavior in fluorescence studies and a more sensitive detection
during fluorescence measurements was detected. A “turn on” of the analyte. The selective detection and enrichment of TNT,
effect with an increasing of the fluorescence response was also a well-known explosive, was performed by using PCN-224.[178]
PCN-224 is based on a six connected Zr-cluster and TCPP
(TCPP = tetrakis(4-carboxylphenyl)-porphyrin) as ligand.[193]
The authors explain the specific detection of TNT with PCN-224
through the hydrophobic character of TNT, in contrast to other
explosive analytes (e.g., TNP).[178] Thereby a preferred interac-
tion with the also hydrophobic TCPP ligand molecule arises,
which lead to a stronger hydrogen interaction. A higher degree
of TNT trapped in the pores and a more sensitive detection of
the analyte is possible. Zhou and co-workers observed a more
sensitive detection of TNP and 4-nitrophenol (NP) in contrast
to, e.g., 2,4-DNT or 2,6-DNP by using BUT-12 (BUT = Beijing
University of Technology) (Zr6O4(OH)8(H2O)4(CTTA)8/3,
CTTA = 5′-(4-carboxyphenyl)-2′,4′,6′-trimethyl-[1,1′:3′,1″-
terphenyl]-4,4″-dicarboxylate), and BUT-13 (Zr6O4(OH)8(H2O)4
(TTNA)8/3, TTNA = 6,6′,6″-(2,4,6-trimethylbenzene-1,3,5-triyl)
tris(2-naphtholate)).[183] In further studies, they prove a prefer-
ential adsorption of TNP and NP out of the analyte solution
into the pore system of the MOF detector material and show a
preconcentration effect.
6. Conclusions and the Future of MOFs in

Hazardous Gas Adsorption
The recent progress in using MOFs for gas enrichment and
sensing described in this review shows the high potential
impact of these materials for hazardous gas adsorption, filtra-
tion, and detection.
In particular, the adsorption and filtration of inorganic,
polar analytes such as ammonia, hydrogen sulfide, and nitric
Figure 20. Structures of various explosives. oxide by MOFs having unsaturated open metal sites or special
functionalities at the organic ligand directing to the inner pore With respect to hazardous gas enrichment, mainly in order
do perform very well for filtration of the mentioned toxic gases. to increase sensor sensitivity and selectivity, the MOFs show
These polar inorganic analytes usually adsorb by chemisorp- a high potential to overcome current limits in the established
tion or chemical reaction rather than physisorption. Therefore, sensor systems. The MOFs for sensor applications were
the MOF filtration media are not necessarily regenerable. The investigated intensively in recent years, as are acknowledged
adsorption of chlorine by the MOFs is only rarely described by detailed reviews. Thus the focus herein was not to repli-
to date. However, results from the literature studying MOFs cate these reviews, but rather to looking at publications which
for chlorine filtration show that chlorine does not preferen- focus on enrichment and sensing of trace and hazardous
tially adsorb onto MOFs with open metal sites, but functional gases that are discussed in the present review. Although
groups like NH2 show a positive effect on chlorine adsorp- MOFs show great potential for trace gas enrichment, espe-
tion. For hydrogen cyanide as well as for phosphine removal cially for polar analytes, not many publications are avail-
only limited research using MOFs is available, probably due to able. In regard to respiratory protection, indoor and cabin
the challenging hazards in the laboratory. The few publications air, the MOFs have been evaluated for organic phosphonates
that do exist show that MOFs, in particular MOF-74, do not and VOC enrichment. In any case, MOFs outperform estab-
surpass the performance of HCN adsorption by (impregnated) lished materials like TenaxTA and Carbosieve. The MOFs
activated carbons under relevant conditions, i.e., in presence of for trace and toxic gas sensing are mainly based on optical
water vapor. For the toxic gas arsine and the radioactive radon changes like luminescence, mechanical sensors (e.g., QCM)
it is shown that MOFs show good potential for filtration and or changes in resistivity (e.g., in combination with semicon-
adsorption. ducting materials). Luminescent MOFs show high potential
Beyond these more or less polar inorganic toxic analytes, to differentiate between various analyte properties (e.g., mol-
MOF adsorption performance has been investigated for ecule size, aromatic character). Even heterostructures, which
some compounds from the substance class of VOCs (e.g., combine the advantage of (luminescent) MOFs and semicon-
cyclohexane, benzene, toluene, halogenated and aliphatic ductor metal oxides, improve the gas monitoring properties
hydrocarbons). It was shown that some MOFs do outperform for hazardous gases like formaldehyde. Research on MOFs
reference materials such as activated carbons in VOC adsorp- integrated in chemiresistive sensors and/or showing conduc-
tion. Key aspects for adsorption performance are the polarity of tivity has increased in interest in recent years. MOFs have
the analyte and the concentration range over which the MOF been investigated as sensors for VOCs, inorganic toxic gases,
is required to operate. For filtration in ambient conditions, and explosives at relevant analyte concentration. Following
the adsorber performance always needs to be tested in the the publications, the MOFs show great potential to enhance
presence of humidity. Some of the aforementioned investiga- desired properties of the sensor devices like sensitivity, selec-
tions of VOC filtration have been done under conditions that tivity, and response time.
do show the high performance of MOFs for VOC adsorption. The key advantage of the MOF adsorbents is the ability to
Due to the wide variety of VOCs which might be encountered, achieve a high degree of selectivity by either choosing the mate-
it is challenging to define which certain characteristics of MOFs rial suited for the specific target from the library of >10.000
enhance the adsorption performance. MOF structures reported of the last two decades or by a more
In regard to filter applications one always needs to con- rational fine tuning using rational concepts such as linker
sider the analyte concentration, polarity, and size as well as design, metal-doping or innovative concepts of cooperative
adsorption temperature and flow rate of the gas. Considering adsorption.[194,195]
real applications, coadsorption of humidity needs to be taken
into account as well. There is still a lack of research consid-
ering relevant application conditions. While respiratory pro-
tection requires no regeneration, for indoor air quality and
Conflict of Interest
cabin air filtration regenerability and cycle testing are manda- The authors declare no conflict of interest.
tory. Applied research should focus on these aspects as well in
order to establish MOFs for relevant applications for environ-
mental comfort and safety. A given MOF often shows a highly
specific and promising performance against certain chemi-
Keywords
cals while current impregnated carbons provide broad spec- adsorption, air purification, metal–organic frameworks, sensors, trace
trum protection from a single filtration medium. Coupled gas enrichment
with the ongoing challenges from moisture stability (which
Received: August 17, 2017
is of paramount importance for this application), it can be
Revised: December 15, 2017
seen that significant hurdles remain before MOFs might be Published online: June 19, 2018
considered as an alternative to impregnated activated carbon.
What might be more feasible in the near term future is for
MOFs to find a role as an additive to activated carbon, and
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Air Purification www.advmat.de

Adsorption and Detection of Hazardous Trace Gases

development for an ever increasing popu-

Advanced sensor characteristics like sensitivity, selectivity,

Formaldehyde 0.1 mg m−3 (30 min) Ammonia 2500 12.5

Styrene 70 µg m−3 (30 min) Cyanogen chloride 300 2

Tetrachloroethylene 0.25 mg m −3 Cyclohexane 2600 10

Toluene 1 mg m−3 (30 min) Formaldehyde 500 1

Table 3. Workplace concentrations of selected explosives.[24–30]

Chemical NOISH REL [mg m−3] OSHA PEL [mg m−3]

4.2. Volatile Organic Compounds

Cyclohexane is included in both the NIOSH APR and EU

C 8 aromatic Structure Kinetic diameter van der Waals volume × 103

o-xylene 0.74 nm 119.91 nm³

m-xylene 0.71 nm 120.04 nm³

ethylbenzene 0.67 nm 120.20 nm³

4.2.5. Halogenated and Noncyclic Hydrocarbons

The adsorption of the C5–C8 alkanes on MIL-101 and a com-

5. Trace Gas Enrichment and Sensing

Ammonia 0.006 0.105b) 0.093 0.042 0.087 0.023 0.001 105

Tetrahydrothiophene 0.001 0.007 0.090 <0.001 0.351b) 0.084 0.123 2.85

Benzene 0.002 0.056 0.096 0.001 0.176b) 0.109 0.155 1.14

Dichloromethane <0.001 0.001 0.032 <0.001 0.055b) 0.019 0.053 1.04

revealed clear groupings of the data by functional groups with

5.2.2. Inorganic Hazardous Trace Gases

Ammonia is a colorless, volatile, and corrosive gas with a pun-

6. Conclusions and the Future of MOFs in

[3] S. K. Brown, Indoor Air 1999, 9, 209. in Effect, https://www.cdc.gov/niosh/npg/nengapdxg.html

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