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MINIREVIEW
Xu et al.
Photocatalytic reduction of CO2: a brief review on product analysis and
systematic methods
 Analytical
Methods
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Photocatalytic reduction of CO2: a brief review on

product analysis and systematic methods†
Cite this: Anal. Methods, 2013, 5, 1086

Jindui Hong, Wei Zhang, Jia Ren and Rong Xu*

Received 25th October 2012
Accepted 14th December 2012
DOI: 10.1039/c2ay26270c
www.rsc.org/methods
Photocatalytic reduction of CO2 for fuels production by using solar energy is an attractive process to
address both energy and environmental issues. Currently, it is still a great challenge to control the CO2
reduction pathways. As a result, many possible chemicals could be present in the reaction products,
ranging from CO, CH4 to higher alkanes in the gas phase, and oxygenates in the liquid phase such as
alcohols, aldehydes and carboxylic acids. A thorough and accurate determination of products is of
critical importance for the evaluation of photocatalyst performance. However to date, only very few
studies have paid attention to the screening of reduction products, and more comprehensive and
standard analysis methods are not yet reported in the literature. In this review, different analysis
methods reported so far are summarized. At the same time, we also developed one set of techniques
involving (1) the design of a two-channel-three-detector gas chromatography system for gaseous
product analysis in the presence of a high concentration of CO2 and alcohols analysis in the liquid
phase, and (2) a high performance liquid chromatography system for the analysis of aldehydes and
carboxylic acids in the liquid phase. The effect of commonly used organic additives as well as alkaline
conditions on liquid phase analysis was also investigated for the first time.

1 Introduction CO2 emissions using carbon-neutral energy sources. The

Fossil fuels are currently the major energy source and are
rapidly consumed to supply the increasing energy demands of
mankind. CO2, an inevitable product of fossil fuel combustion,
leads to possible climate change and may pose a serious impact
on our environment. There is an increasing need to mitigate
School of Chemical & Biomedical Engineering, Nanyang Technological University, 62
Nanyang Drive, 637459 Singapore. E-mail: rxu@ntu.edu.sg; Fax: +65-67947553; Tel:
+65-67906713
† Electronic supplementary information (ESI) available: Chromatographic
conditions. See DOI: 10.1039/c2ay26270c
possibility of CO2 conversion including chemical trans-
formation, photocatalytic reduction, electrochemical reduction,
biological conversion, etc., has been well documented in liter-
ature, such as in several review articles.1–5 Among these,
conversion of CO2 to value-added fuels or chemical products by
direct use of sunlight is an attractive but a challenging process.
CO2 is a rather inert compound and its conversion to other
carbon compounds is generally thermodynamically unfavor-
able. The research on photocatalytic reduction of CO2 is still at
an early stage, despite the recent renewed interest from the
scientic community and certain progress attained in the

Jindui Hong obtained his B.Eng Wei Zhang received his B.Sc in
in 2008 from Xiamen University. 2007 from Peking University and
In 2009, he joined Prof. Rong his Ph.D from Nanyang Techno-
Xu's group as a Ph.D student at logical University under the
Nanyang Technological Univer- supervision of Prof. Rong Xu.
sity. His research is focused on Currently he is a research fellow
photocatalyst development for at Nanyang Technological
water splitting and carbon University. His general research
dioxide reduction. interest is the application of
photocatalysts for solar energy
conversion.

1086 | Anal. Methods, 2013, 5, 1086–1097 This journal is ª The Royal Society of Chemistry 2013
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direction of CO2 reduction and utilization.6–12 It is notorious (in the form of organic species) is irradiated, the amount of
that the efficiencies of photocatalytic CO2 reduction reported so carbon containing products formed from these carbon residues
Published on 20 December 2012. Downloaded by Indian Institute of Science Education and Research Mohali on 2/21/2024 9:49:04 PM.

far are very low. This certainly exerts stress in product identi-
cation and quantication. Hence, many groups have practically
adopted the routine analysis of one or two products in either gas
or liquid phase for evaluation of photocatalytic efficiencies.
CO2 photoreduction involves multi-electron processes which
can lead to a large variety of products ranging from CO, CH4 to
higher hydrocarbons in the gas phase, and various oxygenates
in the liquid phase such as alcohols, aldehydes and carboxylic
acids. A few representative reactions leading to gas and liquid
products are shown in Table 1. The identication and quanti-
cation of as many as possible of such products are essential for
more accurate evaluation of the photocatalytic performances for
the design of better photocatalysts. Furthermore, at the current
stage of research, analysis techniques with low detection limits
are also important to identify the inuence of carbon residues
originating from photocatalyst synthesis which can possibly
contribute to the reduction products.13 As a simple illustration,
if 0.1 g of photocatalyst which contains 1% of carbon residues
could be of the magnitude of a few tens of micromoles, which is
far greater than many reported values attributed to photore-
duction of CO2 in the current literature. In a recent review by
Izumi, it was concluded that those reduction products with
relatively high yields without careful verication may not be
totally produced from CO2.14 While our research efforts are
devoted to developing efficient photocatalyst systems, several
important issues with regards to the product analysis of CO2
reduction need to be urgently addressed:
(1) Can the most likely occurring reduction products be detec-
ted accurately? A reliable conclusion on photocatalytic activities
can only be drawn aer accurate quantication of the products and
elimination of the contribution from carbon contamination.
(2) Will the presence of organic additives affect the product
analysis? Organic additives are oen used as sacricial
reagents, solvents, photocatalysts or photosensitizers, espe-
cially in homogeneous molecular systems. Their effects on the
analysis of CO2 reduction products need to be investigated.

Table 1 CO2 reduction products and corresponding reduction potential with reference to NHE at pH 7

Product Reaction E0redoxa (V vs. NHE)

Oxygen H2O / 0.5O2 + 2H+ + 2e
0.82

Methane CO2 + 8H+ + 8e
/ CH4 + 2H2O
0.24
Ethane 2CO2 + 14H+ + 14e
/ C2H6 + 4H2O
0.27
Carbon monoxide CO2 + 2H+ + 2e
/ CO + H2O
0.51
Methanol CO2 + 6H+ + 6e
/ CH3OH + H2O
0.39
Ethanol 2CO2 + 12H+ + 12e
/ C2H5OH + 3H2O
0.33
1-Propanol 3CO2 + 18H+ + 18e
/ CH3CH2CH2OH + 5H2O
0.31
2-Propanol 3CO2 + 18H+ + 18e
/ CH3CH(OH)CH3 + 5H2O
0.30
Formaldehyde CO2 + 4H+ + 4e
/ HCHO + H2O
0.55
Acetaldehyde 2CO2 + 10H+ + 10e
/ CH3CHO + 3H2O
0.36
Propionaldehyde 3CO2 + 16H+ + 16e
/ CH3CH2CHO + 5H2O
0.32
Acetone 3CO2 + 16H+ + 16e
/ CH3COCH3 + 5H2O
0.31
Formic acid CO2 + 2H+ + 2e
/ HCOOH
0.58
Acetic acid 2CO2 + 8H+ + 8e
/ CH3COOH + 2H2O
0.31
a
Reduction potentials are calculated by using the Gibbs free energy of formation from tabulated thermodynamic data.15

Jia Ren received her B.Sc in 2006 Rong Xu received her Ph.D
from Xidian University and her degree in Chemical Engineering
Ph.D from Shanghai Institute of (2004) from National University
Ceramics, Chinese Academy of of Singapore. She joined the
Sciences in 2011. She worked as School of Chemical & Biomed-
a research fellow at Nanyang ical Engineering, Nanyang
Technological University during Technological University in
2011–2012, focusing on the 2004 and she is currently an
development of photocatalysts Associate Professor there. Her
for carbon dioxide reduction. main research focuses include
the development of semi-
conductor photocatalysts for
solar energy conversion, and
fabrication of nanostructured materials for biomedical and envi-
ronmental applications.

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(3) Do the detected products truly originate from the reduc- 2.2 Method developed by our group
tion of CO2? Techniques like 13C nuclear magnetic resonance
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The analysis of CO2 and products in the gas phase was per-
(NMR) and gas chromatography-mass spectroscopy (GC-MS)
formed using an online GC equipped with a TCD, FID and
can be used for verication.
a methanizer which contains a Ni catalyst. Standard gases
Herein, we focus on the product analysis for photocatalytic
(CO2, H2, N2, CH4, CO and CH3CH3) of high purities and gas
reduction of CO2. Several analysis techniques based on both
mixtures prepared from these standard gases were charged to
literature and our own work are discussed and compared. One
the photoreactor system as the gas samples. Fig. 1 shows the
set of methods is proposed for the analysis of a wide range of simplied conguration of our GC. Helium (99.9995%) was
photoreaction products in gas and liquid phases with low used as the carrier gas. The back channel of GC is equipped
detection limits. The effects of the most commonly used organic
with two packed columns, Hayesep Q and Molsieve 5 Å, and
additives were also investigated. Though the analysis methods
three gas switch valves, V1–V3. During the analysis, 0.25 mL of
discussed and proposed here are in the context of photocatalytic
gas sample in the sample loop of V1 was introduced to the
reduction of CO2, they are also applicable for other CO2
Hayesep Q column where CO2 was separated from the other
reduction processes, such as electrochemical reduction, chem-
gases due to its longer retention time. The other gases can be
ical conversion, biological transformation and so on. It is hoped
completely eluted from the rst column and enter the Mol-
that this report can offer simple guidance to researchers in this sieve column before 2.5 min. At 2.5 min, Valve 2 is switched
community with standard analysis methods for CO2 conversion for CO2 to bypass the Molsieve column and be detected by
reactions.
TCD. Aer TCD analysis, CO2 is vented out by the switch of
Valve 3 during 3–7 min. The rest of the gases aer the Hayesep
Q column were further separated by the Molsieve 5 Å column.
2 Analysis of gas phase products At 10 min, V2 is switched back for these separated gases to be
2.1 Brief review of literature methods detected by TCD and then CH4, CO and CH3CH3 were further
detected by FID with higher sensitivities. The role of the
CH4 and CO are the major gaseous products of CO2 photore- methanizer (nickel catalyst) is to convert CO to CH4 for FID
duction while H2 and/or O2 may also be produced as by- analysis, while alkanes remained unaffected. During this
products from water splitting.9,11,16 In addition, Varghese et al. process, the GC oven was held at 60  C for 15 min and
reported the presence of higher alkanes as the photoreduction increased to 180  C for 5 min for the post-run. The detailed
products of CO2.17 Besides the products, CO2 as the main program can be found in the ESI.†
species in the gas phase due to a low conversion needs to be The volume of our photoreactor circulation system is around
quantied to determine the reaction progress and/or the
1.0 L. The calibration lines of individual gases (CH4, CH3CH3,
extent of CO2 dissolution in the liquid phase.18 Infrared
CO and CO2) are shown in Fig. 2A–D. All these data points are
spectroscopy (IR) or diffuse reectance infrared Fourier well tted to a straight line as indicated by the R2 values of close
transform spectroscopy (DRIFT) has been occasionally to unity. Typical GC chromatographs from TCD and FID for
employed to verify the consumption of CO2 and the generation analysis of a gas mixture containing N2, O2, CH4, CH3CH3, CO
of CO.13,19–22 GC is by far the most commonly used method for and CO2 are shown in Fig. 2E. It can be seen that a good
quantication of these gas species.16,18,23–33 Besides GC, GC-MS separation was achieved. Furthermore, the method detection
was also used for routine analysis of CH4 and CO34–36 or for
carbon source verication.30,37,38 Although a thermal conduc-
tivity detector (TCD) was the only detector used in GC as stated
in some reports, it is suggested that a ame ionization detector
(FID) should be used in order to achieve higher sensitivities for
detection of low concentrations of CO and hydrocarbons.39 FID
analysis is a destructive method. Therefore, the gas should
rst be analyzed by TCD for gases quantication followed by
FID for the analysis of CO and alkanes. Many types of column
have been used, such as molecular sieves,16,28–32,38,40–61 carbon
columns,19,24,26,37,62–70 Poraplot Q40,42–44,61,71–75 and Al2O3.27 It has
been noted that if a high concentration of CO2 remains in the
gas product stream, it can cause deactivation of the nickel
catalyst in the methanizer and certain types of columns,
including the most commonly used molecular sieve column,
making frequent column regeneration necessary.30 Herein, a
better design of GC conguration is proposed to separate and
detect all the gases including CH4, CH3CH3, CO, CO2, O2, N2
and H2 with low detection limits as well as to avoid regular Fig. 1 The flow chart of gas chromatography for gas phase product analysis and
column regeneration and achieve longer lifetimes of the liquid phase analysis of alcohols. V1–V3: gas switch valves, and CL1–3: separation
methanizer and detector. columns.

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Fig. 2 GC calibration lines of gas standards, (A) CH4, (B) CH3CH3, (C) CO, (D) CO2,
and (E) GC curves (green: TCD signal with peaks 1–5; blue: FID signal with peaks
6-mixture, (1) CO2 (2989.0 mmol L
1), (2) O2 (198.2 mmol L
1), (3) N2 (499.2 mmol
L
1), (4) CH4 (33.0 mmol L
1) and (5) CO (44.0 mmol L
1), (6) CH3CH3 (1.1 mmol
L
1), (7) CH4 (33.0 mmol L
1) and (8) CO (44.0 mmol L
1) of standard gas.
limit (MDL) in our system was obtained by following the
procedures described in the US EPA method.76 The obtained
MDLs for CO2, CO, CH4 and CH3CH3 are as low as 2.6, 0.07, 0.03
and 0.004 mmol L
1, respectively.
The automatic sampling system has several advantageous
features: (1) the auto-sampling loop in the rst switch valve can
realize online product analysis and ensure a consistent volume
of gas introduced to the column, (2) the use of the second switch
valve protects the Molsieve 5 Å column from the high concen-
tration of CO2, to avoid frequent regeneration of the column,
and (3) the third switch valve protects the methanizer from the
high concentration of CO2. CO2, if not vented, can also be
converted to CH4 by the methanizer. However, a high concen-
tration of CO2 will lead to rapid deactivation of the Ni catalyst.
Unlike other systems without the vent valves, this design can
greatly enhance the lifetimes of both the column and
methanizer.
Some research groups, such as those of Anpo,35,79–81 Zou23,82,83
and Ye,84–86 adopted the gas phase reaction for CO2 photore-
duction. In a typical gas phase reaction, the solid photocatalyst
was initially well dispersed at the bottom of the reactor which
contains CO2 gas, followed by injecting a small amount of liquid
water (e.g. 1 mL). Under a low pressure condition, liquid water
vaporizes and mixes with CO2 gas. In these cases, the analysis
methods proposed above can be used for accurate analysis of
gas products. Gas phase reduction was also carried out using
H2 67–69 or CH4 87,88 instead of water to reduce CO2. For these
water free gas–solid systems, a GC-based method is still widely
used for the quantication of products. Nevertheless, it is worth
noting that in situ DRIFT coupled with isotopically labeled
13
CO2 can be employed to monitor the intermediates or
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Analytical Methods
products adsorbed on the solid photocatalyst surface.13,19,22 For
example, Yang et al. used a cell equipped with three windows
(two for IR transmission and one for light irradiation) to hold
the photocatalyst and a spectrometer with a liquid N2-cooled
mercury cadmium telluride (MCT) detector to record the
spectrum.13 Real-time spectra can be collected at different
irradiation times to verify the intermediates during CO2
reduction. Such a technique is useful for mechanistic studies.
3 Analysis of liquid phase products
3.1 Brief comparison of various techniques
Although GC with TCD/FID is still the main technique used for
the analysis of different types of liquid oxygenates (mainly
alcohols),18,19,27,28,30,32,34,40,42,48–50,53,71,89–105 several other methods
have been utilized, including GC-MS,35,43,106 high performance
liquid chromatography (HPLC),18,38,55–57,62,77,99,107 ion exchange
chromatography (IEC),16,18,26,30,41,51,64,73,108–113 ultraviolet-visible
(UV-Vis) spectroscopy (colorimetric assay) aer reacting with
chromotropic acid40,42,44,46,50 or Nash reagent27,29,96,97,114–116 and
NMR.31,117 The compounds that can be analyzed and their
detection limits using various techniques, together with the
associated limitations, are summarized in Table 2.
3.2 Alcohols analysis
Based on the literature, alcohols, especially methanol, are
frequently detected products from CO2 photoreduction in the
liquid phase. GC with a FID works well for the analysis of
alcohols, and several kinds of columns have been used such as
HP-5,34,40,42,50 Porapak Q,27,90–92 DB-WAX30,93 and PEG
columns.32,71,89 In this work, alcohols up to C3 including meth-
anol, ethanol, 1-propanol and 2-propanol in the liquid phase
were analyzed by GC with a FID, a DB-WAX column and helium
as the carrier gas. The liquid sample was rst ltered with a
PTFE lter to remove solid particles before auto-injection of
1.0 mL of the clear solution into the GC. It was found that the
lter membrane has no effect on the concentrations of chemical
species in the liquid phase.
The GC oven was initially held at 40  C for 5 min, then ramped
to 180  C with a heating rate of 20  C min
1 and held at this
temperature for 3 min to eliminate the water vapor in the liquid
sample from the column. Fig. 3A–D shows the calibration lines of
methanol, ethanol, 1-propanol and 2-propanol standards in
aqueous solutions. The data points can be well tted to a straight
line with R2 values close to unity. A typical GC graph from anal-
ysis of an aqueous mixture of the four alcohols is shown in
Fig. 3E. Using the current method, 2-propanol (Peak 2) and
ethanol (Peak 3) signals are overlapped due to their similar
polarities and boiling points (82.5  C and 78  C). This problem
can be overcome by using a longer column or reduced carrier gas
ow (data not shown). The MDLs obtained by the current method
for methanol, ethanol, 1-propanol and 2-propanol in aqueous
solutions were 3.5, 3.3, 2.3 and 1.7 mmol L
1, respectively.
In many studies, organic compounds have been engaged in
photoreduction of CO2 for various reasons such as sacricial
reagents (e.g., methanol, triethanolamine),38,41,56,99 solvents (e.g.,
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Table 2 Comparison of techniques used for liquid phase analysis in CO2 photoreduction
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Technique Compounds Detection limit Limitations

GC Alcohols 3 mmol L
1a Much higher detection limits for

Aldehydes 100 mmol L
1 30 aldehydes
HPLC Carboxylic acids77 5 mmol L
1a Aldehydes need to be derivatized
Aldehydes18,78 0.07 mmol L
1a before analysis
IEC Carboxylic acids 0.1 mmol L
1 for HCOOH30 For acids only
10 mmol L
1 for CH3COOH30
UV-Vis HCHO aer reaction with Nash's 0.17 mmol L
1a Not applicable for other aldehydes
reagent or HCOOH 0.08 mmol L
1a and acids; HCOOH can only be
analyzed when no other organics
are present
1
H or 13C NMR All oxygenates31 Not available High cost, difficult for
quantication although some work
demonstrated quantication,31
mainly for product qualication,
carbon source verication
GC/LC-MS All oxygenates Not available Mainly for product qualication,
carbon source verication
a
Approximately the average value of the MDLs obtained for standard samples analyzed in this work following the US EPA method. MDL of
individual compounds can be found in Fig. 9.

triethylamine (TEA), methyl viologen (MV), Rose bengal (RB) and

[Ru(bpy)3]Cl2. In addition, the effect of alkaline conditions,
adjusted using NaOH, was investigated. The concentrations of
alcohols were kept at 1 mL L
1. The results shown in Table 3 and
Fig. 4 indicate that alcohol analysis is very sensitive to most of the
organics in terms of peak areas. In addition, as shown in Fig. 4,
many extra peaks can be detected due to the presence of the
organic compounds in the case of MV, ACN, DMF, TEOA and
TEA. The interaction of these compounds with the column and
their interference with alcohols result in the complicated spectra
of GC signals. In fact, to the best of our knowledge, examples of
alcohol quantication when organics are involved in CO2
reduction are rare. GC-MS and/or NMR techniques may be used
for qualitative analysis of alcohols when the use of organics is
unavoidable. When only a simple alkaline condition was applied
by adding NaOH, the peak positions and areas for all the four
alcohols remained almost unchanged, except for around a 10%
increase in the peak area of 1-propanol.

Table 3 Effects of various organic compounds and alkaline condition on the GC

peak areas of alcohols (1 mL L
1)a
Fig. 3 GC calibration lines of alcohol standards in aqueous solution, (A) methanol,
(B) ethanol, (C) 1-propanol, and (D) 2-propanol, and (E) a typical GC curve of an
aqueous mixture of alcohol standards, (1) methanol (24.8 mmol L
1), (2) 2-propanol
Medium Methanol Ethanol 1-Propanol 2-Propanol
(13.1 mmol L
1), (3) ethanol (17.2 mmol L
1), and (4) 1-propanol (13.4 mmol L
1).
H2O 5.7 9.0 9.0 8.6
ACNb 45.1 9.6 15.3 8.6
DMFb 36.9 11.0 5.0 8.3
acetonitrile, dimethylformamide),38,118 photocatalysts (e.g., Ru TEOAb 14.1 10.4 8.9 9.6
complexes)6,7 or photosensitizers (e.g., N3 dye, Rose bengal).119 TEAb 58.6 21 4.6 9.1
MVc 93.9 6.2 7.2 8.2
The presence of such organic compounds in the reaction systems
RBc 6.1 14.0 10.3 8.4
may affect the product analysis in the liquid phase. In this study, [Ru(bpy)3]Cl2c 4.9 7.4 9.4 7.9
the inuence of several commonly used organic species was NaOHd 5.4 9.2 10.0 8.9
investigated for liquid phase analysis. Table 3 lists the effects of a
Equivalent to 24.8 mmol L
1 of methanol, 17.2 mmol L
1 of ethanol,
the organic additives on alcohol analysis including acetonitrile 13.4 mmol L
1 of 1-propanol and 13.1 mmol L
1 of 2-propanol. b 15 v
(ACN), dimethylformamide (DMF), triethanolamine (TEOA), %. c 0.1 mM. d 0.1 M.

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Fig. 4 GC peaks of methanol, ethanol, 1-propanol in (A) 0.1 M NaOH, 0.1 mM MV, 0.1 mM RB, 0.1 mM [Ru(bpy)3]Cl2, and (B) 15 v% ACN, 15 v% DMF, 15 v% TEA, 15 v
% TEOA; GC peaks of 2-propanol in (C) 0.1 M NaOH, 0.1 mM MV, 0.1 mM RB, 0.1 mM [Ru(bpy)3]Cl2, and (D) 15 v% ACN, 15 v% DMF, 15 v% TEA, 15 v% TEOA.

3.3 Aldehydes analysis rotary evaporator was used to remove the solvent of the
collected methylene chloride layers. The dried solid was then
Aldehydes are another group of possible reduction products.
dissolved in 5 mL of ACN and analyzed by HPLC with a
Although less frequently detected and reported in literature,
Eclipse Plus C18 column, a variable wavelength detector
analytical techniques need to be developed for CO2 reduction
(VWD) at 360 nm and 60 v% ACN in H2O as the mobile phase.
product screening. Besides Nash's colorimetric method,49,120
More details about the method can be found in the ESI.† The
others also used GC with either TCD/FID with a Porapak T
calibration lines of various aldehydes aer derivatization with
column27,28 or FID with a DB-WAX column30 and BX-10 column38
to quantify aldehydes. However, the detection limits DNPH are shown in Fig. 5A–D with their R2 values very close
to unity. A typical HPLC curve of the mixture of these four
(100 mmol L
1) are about 2 orders of magnitude higher than
derived compounds (Fig. 5F) shows well separated peaks. The
those of alcohols. Hence, only relatively concentrated aldehydes
MDLs of this method were found to be very low at around
can be analyzed by the GC method, while the concentrations of
0.03–0.08 mmol L
1.
aldehydes in the liquid phase of CO2 photoreduction are usually
The DNPH derivatization method discussed above is rela-
much lower than such detection limits. In this work, C1–C3
tively time consuming. As a result, it is suggested that this
aldehydes (formaldehyde, acetaldehyde, propionaldehyde and
method could be applied mainly to verify whether aldehydes
acetone) were analyzed by HPLC aer derivatization with 2,4-
dinitrophenylhydrazine (DNPH). Although this derivatization are produced in the liquid phase. If formaldehyde is the only
product veried by this method, Nash's method is much more
method has been widely used for aldehydes analysis in ambient
convenient for routine analysis.120 Nash reagent was prepared
air, cigarette smoke, drinking water, etc.,78 only one recent study
by adding 25 g of ammonium acetate, 2.1 mL of acetic acid
has adopted it for the quantication of aldehydes in CO2
and 0.2 mL of acetylacetone into water and making the total
reduction, and more detailed investigation, such as the effect of
volume of the solution 100 mL. Then 2 mL of liquid sample
organics, has not yet been performed.18 Herein, the DNPH
was mixed with 2 mL of Nash reagent and shaken for 1 h. The
derivatization was performed according to a modied US EPA
nal solution was analyzed by UV-Vis spectroscopy and the
method 8315A.121
Briey, 50 mL of the liquid sample was added with 10 mL absorbance at 414 nm was used for quantication. The cali-
bration line of formaldehyde by this method is shown in
of citrate buffer (pH ¼ 5) followed by the addition of 2 mL of
Fig. 5E and the MDL obtained is 0.17 mmol L
1. Another
DNPH (5 mM in methanol). The mixture was shaken at 40  C
colorimetric method, similar to Nash's method, uses chro-
for 2 h followed by adding 20 mL of methylene chloride to
motropic acid (4,5-dihydroxynaphthalene-2,7-disulfonic acid,
extract the derivatized aldehyde–DNPH product three times. A
disodium salt dehydrate) as the color reagent and the

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Analytical Methods Minireview

Table 4 Effects of various organics and alkaline condition on the HPLC peak
areas of aldehydes (10 mmol L
1)
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Medium FADd AADe ACDf PADg

H2O 21.8 20.9 22.1 25.7

Methanola 21.4 20.6 22.0 25.6
Ethanola 21.3 20.4 22.2 25.8
1-Propanola 21.1 20.3 21.7 25.3
2-Propanola 20.2 19.3 20.9 24.3
DMFa 20.4 19.5 21.1 24.5
MVb 20.8 20.3 22.2 25.8
RBb 22.7 21.6 24.3 26.3
[Ru(bipy)3]Cl2b 22.1 21.5 22.0 25.8
TEOAa 20.5 20.3 22.1 25.4
NaOHc — — 18.2 —
TEAa — — 18.6 —
a
15 v%. b 0.1 mM. c 0.1 M. d Formaldehyde–DNPH. e
Acetaldehyde–
DNPH. f Acetone–DNPH. g Propionaldehyde–DNPH.

Fig. 5 HPLC calibration lines of aldehydes after 2,4-dinitrophenylhydrazine
(DNPH) derivatization, (A) formaldehyde, (B) acetaldehyde, (C) acetone, (D) pro-
pionaldehyde, (E) UV-Vis calibration curve for formaldehyde after reaction with
Nash's reagent, and (F) HPLC curve of 5 mmol L
1 aldehydes–DNPH standards with
various peaks, (1) formaldehyde–DNPH, (2) acetaldehyde–DNPH, (3) acetone–
DNPH and (4) propionaldehyde–DNPH.
recent work by Cao et al., formic acid was produced from CO2
reduction and 1H NMR was used for quantication by using
CH3COONa as an internal standard.117 However, for routine
analysis, especially the mixture of carboxylic acids in liquid
samples, IEC16,18,26,30,41,51,64,73,108–113 or HPLC
18,38,55–57,62,77,99,107
methods are recommended. Herein, we used
the HPLC method with a PL Hi-Plex H column and VWD
(210 nm) for carboxylic acids analysis.
The mobile phase used was 5 mM H2SO4. The temperature
was set at 55  C and injection volume was 20 mL. More details
about the method can be found in ESI.† The calibration lines of

absorbance at 577 nm was monitored. The detailed method

can be found in the literature.93,122
As discussed above, organics may affect the analysis of
oxygenates. Several organics were added during the prepara-
tion of derived aldehydes–DNPH for HPLC analysis. As shown
in Table 4 and Fig. 6, most of these additives did not affect the
aldehyde analysis, with both retention time and peak area
remaining unchanged. In the case of TEA and NaOH, as
shown in Fig. 6B, only acetone–DNPH in TEA still can be
identied with a slightly smaller peak area and shorter
retention time than those in H2O. No matching peaks can be
found for the other three aldehydes. Low concentrations of
TEA (around 20–30 mM) were oen used as the modier for
the mobile phase of HPLC which typically do not affect the
analysis of organic compounds. However, if TEA concentration
is relatively high, such as 15 v% (equivalent to 1.1 M in this
work), the peak shape and retention time can be affected.123
On the other hand, higher pH (0.1 M NaOH, pH ¼ 13) also
leads to the risk of matrix dissolution of some columns
packed with silica.124

3.4 Carboxylic acids analysis Fig. 6 HPLC peaks of FAD, AAD, ACD, PAD in (A) 15 v% methanol, 15 v%
ethanol, 15 v% 1-propanol, 15 v% 2-propanol, 15 v% DMF, 15 v% TEOA
Carboxylic acids (formic acid and acetic acid) have been found and 0.1 mM MV, and (B) 0.1 mM RB, 0.1 mM [Ru(bpy)3]Cl2, 15 v% TEA and
as the photoreduction products of CO2 in the liquid phase. In a 0.1 M NaOH.

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Minireview Analytical Methods

formic acid and acetic acid are shown in Fig. 7A and B, of acids. In the case of TEOA, the effect was mainly due to the
respectively with well tted straight lines. A typical HPLC curve raised of the baseline caused by the tail of the TEOA peak.
Published on 20 December 2012. Downloaded by Indian Institute of Science Education and Research Mohali on 2/21/2024 9:49:04 PM.

is shown in Fig. 7D indicating a good separation of these two
acids. In the HPLC curve, water solvent peaks (marked by
asterisks) are also present. The obtained MDLs for HCOOH and
CH3COOH in the aqueous solution were 3.9 and 6.3 mmol L
1,
respectively. When HCOOH is the only organic species present
in the liquid phase, UV-Vis spectroscopy can be used for
quantication. The liquid sample aer removal of the solid
particles can be directly analyzed by measuring the UV absor-
bance at 210 nm.
The calibration curve obtained by this method is shown in
Fig. 7C with a low detection limit of 0.08 mmol L
1. Although
this method is simple for HCOOH analysis, it has a limitation
since it can only be used for quantication of HCOOH in water
in the absence of other organic species. Alternatively, when
HCOOH is the only carboxylic acid product, colorimetric
methods can also be used aer reducing HCOOH to HCHO122
and then reacting with chromotropic acid93 or Nash
reagent.49,125 Briey, 0.5 mL of liquid sample was added into
magnesium powder (50 mg) following by drop-wise addition of
0.5 mL 37% hydrochloric acid (10 M) at 0  C and then 3 mL 1
M NaOH. The resultant suspension was centrifuged at 13 000
rpm for 5 min and 2 mL of supernatant was mixed with 2 mL
of Nash reagent for UV-Vis analysis (see Section 3.3) to deter-
mine the total amount of HCHO. HCOOH can be determined
aer subtracting the amount of HCHO in the product (Nash's
method). Care should be taken that the accuracy of HCOOH
quantication by this method is largely affected by the yield of
reduction. Hence, this method is not suitable for accurate
routine analysis, but may be used for a quick qualitative check
when the identication of HCOOH by other techniques is
obscure. The effects of organics and alkaline conditions on
acid analysis were also studied. The results in Table 5 and
Fig. 8 show that only DMF, TEA and TEOA affected the analysis
Therefore, baseline correction needs to be carried out during
the quantication of HCOOH and CH3COOH when TEOA is
present. When TEA was present, the analysis of HCOOH was
not affected while the peak area of CH3COOH was greatly
enhanced. In the presence of DMF, the baseline raised aer
the HCOOH signal, with the peak area of HCOOH enhanced
and that of CH3COOH unchanged. The retention time in all
cases was kept constant. The interaction of the amine groups
in TEA and DMF with the column materials may cause such an
abnormality.
4 Carbon source verification and O2
monitoring
The contribution of carbon residues to the photoreduction
products has been recently reported.13 The in situ DRIFT study
indicated that 12CO was the main product when 13CO2 gas was
used during surface photoreaction over the Cu(I)/TiO2 catalyst.
The 12C source was proven to be from the carbon residue on
the photocatalyst ,originating from the organics used during
photocatalyst preparation. Based on this, the photocatalytic
activities reported for CO2 reduction in the literature may need
to be veried if there was no tracking of carbon source or
enough evidences for photocatalytic events.14 Thus, either
carefully and systematically designed control experiments, or
carbon source tracking by NMR, GC-MS or LC-MS with isotope
13
C labeled CO2 as the reactant, is necessary. The carbon
source in gas products like methane and carbon monoxide can
be veried by spectroscopic methods (e.g. DRIFT) or GC-MS
and in liquid oxygenates by 13C NMR, GC-MS or LC-MS. For
example, Liu et al. studied the solvent effect on photocatalytic
CO2 reduction by using 13CO2 with GC-MS and 13C NMR to
identify the source of carbon in CO and liquid products,
respectively.38 Yui et al. reported the use of TiO2 (P25) for
methane production. The carbon source of methane was

Table 5 Effects of various organics and alkaline condition on the HPLC peak
areas of acids (10 mL L
1)a

Medium Formic acid Acetic acid

H2O 229 135

Methanolb 229 134
Ethanolb 227 134
1-Propanolb 230 137
2-Propanolb 228 135
ACNb 232 136
MVc 231 138
[Ru(bpy)3]Cl2c 231 139
RBc 226 136
NaOHd 230 136
DMFb 451 131
TEAb 234 306
Fig. 7 HPLC calibration lines of (A) formic acid and (B) acetic acid, (C) UV-Vis
TEOAb 229e 138e
calibration line of formic acid and (D) HPLC curve of a mixture containing 109 mmol
L
1 formic (Peak 1) and 83 mmol L
1 acetic (Peak 2) acid; * denotes water a
Equivalent to 217 mmol L
1 of formic acid and 167 mmol L
1 of acetic
solvent peak. acid. b 15 v%. c 0.1 mM. d 0.1 M. e Aer baseline correction.

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5 Summary
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Based on our studies, major products in both gas and liquid

phases from CO2 photoreduction can be detected accurately with
low detection limits by a combination of GC and HPLC methods.
Fig. 9 summarizes the analysis methods and the detection limits
of the major chemical species in both gas and liquid phases in the
absence of organic additives. The effects of several organic
additives including commonly used solvents, photosensitizers
and sacricial reagents in photoreaction were investigated. It has
been found that alcohol analysis by GC methods is more sensitive
to organic additives while aldehyde and acid analyses by HPLC
methods are not affected by most of the organics investigated.
The importance of carbon source verication is highlighted and
several techniques such as DRIFT, NMR and GC-MS can be used.

Fig. 8 HPLC peaks of formic acid and acetic acid in (A) 15 v% methanol, 15 v%
ethanol, 15 v% 1-propanol, 15 v% 2-propanol, 15 v% ACN, 0.1 M NaOH, 0.1 mM
MV, 0.1 mM [Ru(bpy)3]Cl2 and 0.1 mM RB, and (B) 15 v% DMF, 15 v% TEA and
15 v% TEOA.

conrmed from CO2 based on a signal at m/z ¼ 17 (13CH4) in

GC-MS when 13CO2 was used.30 The photocatalytic activity of a
titanium metal–organic framework in CO2 reduction to
produce formic acid was conrmed by using 13C NMR.41 A Fig. 9 Summary of analysis methods for gas and liquid phase samples. Deriva-
tization: aldehydes were derivatized with DNPH before performing HPLC analysis.
signal at 165.30 ppm can be found, which was assigned to
The detection limits (mmol L
1) are shown in brackets.
HCOO, while such a signal was not found when 12CO2 was
used. In another report, 13C-labeled HCOOH in the product
was found to be easily detected by 13C NMR, to conrm that
the product was from the reduction of CO2 rather than from Abbreviations
other carbon sources on the used carbon nanoparticles.117
Using layered double hydroxides as a photocatalyst, the carbon
source of CO and oxygen source of O2 were also conrmed AAD Acetaldehyde–DNPH
ACN Acetonitrile
from CO2 and H2O respectively by using 13CO2 and H218O with
ACD Acetone–DNPH
GC-MS method.37
CL Column
Finally, when water is used as the reducing agent for CO2,
DMF Dimethylformamide
O2 evolution is an important indicating factor to support
DNPH 2,4-Dinitrophenylhydrazine
photocatalytic CO2 reduction.126 Kudo and co-workers16 DRIFT Diffuse reectance infrared Fourier transform
reported that the production of H2, O2 and CO are stoichio- spectroscopy
metric over Ag loaded ALa4Ti4O15 (A ¼ Ca, Sr, and Ba) FAD Formaldehyde–DNPH
photocatalysts. The ratio of the mole of reacted electrons to FID Flame ionization detector
that of holes was found to be almost unity, indicating that GC Gas chromatography
the CO2 reduction occurred photocatalytically with water as GC-MS Gas chromatography-mass spectroscopy
the reducing agent. To ascertain that O2 is generated from the LC-MS Liquid chromatography-mass spectroscopy
reaction rather than from air contamination, the volumetric HPLC High performance liquid chromatography
(molar) ratio of O2 to N2 over reaction time should be moni- IEC Ion-exchange chromatography
tored. In a recent study, the molar ratio of O2/N2 was found to IR Infrared spectroscopy
gradually increase from 0.26 (the ratio in air) to 0.40 aer light MDL Method detection limit
irradiation. In addition, the trend of this ratio was found to be MV Methyl viologen
similar to that of CH4 production, indicating O2 was produced NMR Nuclear magnetic resonance
by photoreaction.126 PAD Propionaldehyde–DNPH

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Minireview
PTFE Polytetrauoroethylene
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RB Rose bengal
TCD Thermal conductivity detector.
Acknowledgements
This work was supported by National Environment Agency,
Singapore under the Environment Technology Research Pro-
gramme (ETRP) through Project no.: ETRP 1002 103, and
SinBeRISE CREATE Programme from National Research Foun-
dation. We acknowledge Ms Sheue Wen Ong and Mr Mark
Stephen Richards from Agilent Technologies Singapore Pte. Ltd.
for help in the design of GC congurations.
References
1 M. Mikkelsen, M. Jorgensen and F. C. Krebs, Energy Environ.
Sci., 2010, 3, 43–81.
2 Z. Jiang, T. Xiao, V. L. Kuznetsov and P. P. Edwards, Philos.
Trans. R. Soc. London, Ser. A, 2010, 368, 3343–3364.
3 C. Song, Catal. Today, 2006, 115, 2–32.
4 M. Aresta and A. Dibenedetto, Dalton Trans., 2007, 2975–2992.
5 T. Sakakura, J. C. Choi and H. Yasuda, Chem. Rev., 2007,
107, 2365–2387.
6 A. J. Morris, G. J. Meyer and E. Fujita, Acc. Chem. Res., 2009,
42, 1983–1994.
7 E. Fujita, Coord. Chem. Rev., 1999, 185, 373–384.
8 D. C. Grills and E. Fujita, J. Phys. Chem. Lett., 2010, 1, 2709–
2718.
9 V. P. Indrakanti, J. D. Kubicki and H. H. Schobert, Energy
Environ. Sci., 2009, 2, 745–758.
10 M. R. Hoffmann, J. A. Moss and M. M. Baum, Dalton Trans.,
2011, 40, 5151–5158.
11 P. Usubharatana, D. McMartin, A. Veawab and
P. Tontiwachwuthikul, Ind. Eng. Chem. Res., 2006, 45,
2558–2568.
12 S. Roy, O. Varghese, M. Paulose and C. Grimes, ACS Nano,
2010, 4, 1259–1278.
13 C. C. Yang, Y. H. Yu, B. van der Linden, J. C. S. Wu and
G. Mul, J. Am. Chem. Soc., 2010, 132, 8398–8406.
14 Y. Izumi, Coord. Chem. Rev., 2013, 257, 171–186.
15 J. A. Dean, Lange's Handbook of Chemistry, McGraw-Hill,
New York, 1999.
16 K. Lizuka, T. Wato, Y. Miseki, K. Saito and A. Kudo, J. Am.
Chem. Soc., 2011, 133, 20863–20868.
17 O. Varghese, M. Paulose, T. LaTempa and C. Grimes, Nano
Lett., 2009, 9, 731–737.
18 Y. P. Peng, Y. T. Yeh, S. I. Shah and C. Huang, Appl. Catal., B,
2012, 123–124, 414–423.
19 C. J. Wang, R. L. Thompson, J. Baltrus and C. Matranga,
J. Phys. Chem. Lett., 2010, 1, 48–53.
20 W. Lin, H. Han and H. Frei, J. Phys. Chem. B, 2004, 108,
18269–18273.
21 W. Lin and H. Frei, J. Am. Chem. Soc., 2005, 127, 1610–1611.
22 N. Ulagappan and H. Frei, J. Phys. Chem. A, 2000, 104, 7834–
7839.
This journal is ª The Royal Society of Chemistry 2013
View Article Online
Analytical Methods
23 Q. Liu, Y. Zhou, J. Kou, X. Chen, Z. Tian, J. Gao, S. Yan and
Z. Zou, J. Am. Chem. Soc., 2010, 132, 14385–14387.
24 T. W. Woolerton, S. Sheard, E. Reisner, E. Pierce,
S. W. Ragsdale and F. A. Armstrong, J. Am. Chem. Soc.,
2010, 132, 2132–2133.
25 J. Pan, X. Wu, L. Wang, G. Liu, G. Q. M. Lu and H. M. Cheng,
Chem. Commun., 2011, 47, 8361–8363.
26 S. Sato, T. Morikawa, S. Saeki, T. Kajino and T. Motohiro,
Angew. Chem., Int. Ed., 2010, 122, 5227–5231.
27 M. Subrahmanyam, S. Kaneco and N. Alonso-Vante, Appl.
Catal., B, 1999, 23, 169–174.
28 G. Guan, T. Kida and A. Yoshida, Appl. Catal., B, 2003, 41,
387–396.
29 Z. Zhao, J. Fan and Z. Wang, J. Clean. Prod., 2007, 15, 1894–
1897.
30 T. Yui, A. Kan, C. Saitoh, K. Koike, T. Ibusuki and
O. Ishitani, ACS Appl. Mater. Interfaces, 2011, 3, 2594–2600.
31 K. P. Kuhl, E. R. Cave, D. N. Abram and T. F. Jaramillo,
Energy Environ. Sci., 2012, 5, 7050–7059.
32 N. Ahmed, Y. Shibata, T. Taniguchi and Y. Izumi, J. Catal.,
2011, 279, 123–135.
33 C. C. Lo, C. H. Hung, C. S. Yuan and J. F. Wu, Sol. Energy
Mater. Sol. Cells, 2007, 91, 1765–1774.
34 M. A. Asi, C. He, M. Su, D. Xia, L. Lin, H. Deng, Y. Xiong,
R. Qiu and X. Li, Catal. Today, 2011, 175, 256–263.
35 M. Anpo, H. Yamashita, Y. Ichihashi and S. Ehara,
J. Electroanal. Chem., 1995, 396, 21–26.
36 Y. Ku, W. H. Lee and W. Y. Wang, J. Mol. Catal. A: Chem.,
2004, 212, 191–196.
37 K. Teramura, S. Iguchi, Y. Mizuno, T. Shishido and
T. Tanaka, Angew. Chem., Int. Ed., 2012, 51, 8008–8011.
38 B. J. Liu, T. Torimoto, H. Matsumoto and H. Yoneyama,
J. Photochem. Photobiol., A, 1997, 108, 187–192.
39 D. Rood, The Troubleshooting and Maintenance Guide for Gas
Chromatographers, Wiley-VCH, Weinheim, 2007, pp. 147–
148, 166–167.
40 K. Koci, L. Obalova, L. Matejova, D. Placha, Z. Lacny,
J. Jirkovsky and O. Solcova, Appl. Catal., B, 2009, 89, 494–
502.
41 Y. Fu, D. Sun, Y. Chen, R. Huang, Z. Ding, X. Fu and Z. Li,
Angew. Chem., Int. Ed., 2012, 51, 3364–3367.
42 K. Koci, K. Mateju, L. Obalova, S. Krejcikova, Z. Lacny,
D. Placha, L. Capek, A. Hospodkova and O. Solcova, Appl.
Catal., B, 2010, 96, 239–244.
43 Y. Y. Liu, B. B. Huang, Y. Dai, X. Y. Zhang, X. Y. Qin,
M. H. Jiang and M. H. Whangbo, Catal. Commun., 2009,
11, 210–213.
44 Y. Hori, A. Murata and R. Takahashi, J. Chem. Soc., Faraday
Trans. 1, 1989, 85, 2309–2326.
45 H. Hori, K. Koike, Y. Suzuki, M. Ishizuka, J. Tanaka,
K. Takeuchi and Y. Sasaki, J. Mol. Catal. A: Chem., 2002,
179, 1–9.
46 K. Hirano, K. Inoue and T. Yatsu, J. Photochem. Photobiol., A,
1992, 64, 255–258.
47 K. Sayama and H. Arakawa, J. Phys. Chem., 1993, 97, 531–533.
48 T. Inoue, A. Fujishima, S. Konishi and K. Honda, Nature,
1979, 277, 637–638.
Anal. Methods, 2013, 5, 1086–1097 | 1095

Analytical Methods
49 N. Sasirekha, S. J. S. Basha and K. Shanthi, Appl. Catal., B,
2006, 62, 169–180.
Published on 20 December 2012. Downloaded by Indian Institute of Science Education and Research Mohali on 2/21/2024 9:49:04 PM.
50 K. Koci, V. Matejka, P. Kovar, Z. Lacny and L. Obalova,
Catal. Today, 2011, 161, 105–109.
51 I. Willner and D. Mandler, J. Am. Chem. Soc., 1989, 111,
1330–1336.
52 C. C. Yang, J. Vernimmen, V. Meynen, P. Cool and G. Mul,
J. Catal., 2011, 284, 1–8.
53 K. Ogura and M. Takagi, J. Electroanal. Chem., 1986, 201,
359–365.
54 H. Park, J. H. Choi, K. M. Choi, D. K. Lee and J. K. Kang,
J. Mater. Chem., 2012, 22, 5304–5307.
55 H. Inoue, H. Moriwaki, K. Maeda and H. Yoneyama,
J. Photochem. Photobiol., A, 1995, 86, 191–196.
56 B. J. Liu, T. Torimoto and H. Yoneyama, J. Photochem.
Photobiol., A, 1998, 113, 93–97.
57 B. J. Liu, T. Torimoto and H. Yoneyama, J. Photochem.
Photobiol., A, 1998, 115, 227–230.
58 Y. Kohno, T. Tanaka, T. Funabiki and S. Yoshida, Phys.
Chem. Chem. Phys., 2000, 2, 2635–2639.
59 Y. Kohno, T. Tanaka, T. Funabiki and S. Yoshida, Phys.
Chem. Chem. Phys., 2000, 2, 5302–5307.
60 J. M. Lehn and R. Ziessel, Proc. Natl. Acad. Sci. U. S. A., 1982,
79, 701.
61 K. Adachi, K. Ohta and T. Mizuno, Sol. Energy, 1994, 53,
187–190.
62 H. Fujiwara, H. Hosokawa, K. Murakoshi, Y. Wada,
S. Yanagida, T. Okada and H. Kobayashi, J. Phys. Chem. B,
1997, 101, 8270–8278.
63 H. Hori, J. Ishihara, K. Koike, K. Takeuchi, T. Ibusuki and
O. Ishitani, J. Photochem. Photobiol., A, 1999, 120, 119–124.
64 M. Kanemoto, T. Shiragami, C. Pac and S. Yanagida, J. Phys.
Chem., 1992, 96, 3521–3526.
65 Y. Kohno, H. Ishikawa, T. Tanaka, T. Funabiki and
S. Yoshida, Phys. Chem. Chem. Phys., 2001, 3, 1108–1113.
66 H. Takeda, K. Koike, H. Inoue and O. Ishitani, J. Am. Chem.
Soc., 2008, 130, 2023–2031.
67 K. Teramura, S. Okuoka, H. Tsuneoka, T. Shishido and
T. Tanaka, Appl. Catal., B, 2010, 96, 565–568.
68 K. Teramura, H. Tsuneoka, T. Shishido and T. Tanaka,
Chem. Phys. Lett., 2008, 467, 191–194.
69 H. Tsuneoka, K. Teramura, T. Shishido and T. Tanaka,
J. Phys. Chem. C, 2010, 114, 8892–8898.
70 T. W. Woolerton, S. Sheard, E. Pierce, S. W. Ragsdale and
F. A. Armstrong, Energy Environ. Sci., 2011, 4, 2393–
2399.
71 G. Arai, T. Harashina and I. Yasumori, Chem. Lett., 1989,
1215–1218.
72 G. R. Dey, A. Belapurkar and K. Kishore, J. Photochem.
Photobiol., A, 2004, 163, 503–508.
73 H. Fujiwara, H. Hosokawa, K. Murakoshi, Y. Wada and
S. Yanagida, Langmuir, 1998, 14, 5154–5159.
74 F. Solymosi and I. Tombacz, Catal. Lett., 1994, 27, 61–65.
75 X. Zhang, J. Li, X. Lu, C. Tang and G. Lu, J. Colloid Interface
Sci., 2012, 377, 277–283.
76 U.S. Environmental Protection Agency, Part 136, Appendix
B, Revision 1.11, 40 CFR., Ch1, 1986.
1096 | Anal. Methods, 2013, 5, 1086–1097
View Article Online
Minireview
77 S. Kaneco, N. Hiei, Y. Xing, H. Katsumata, H. Ohnishi,
T. Suzuki and K. Ohta, Electrochim. Acta, 2002, 48, 51–55.
78 Y. L. Lin, P. Y. Wang, L. L. Hsieh, K. H. Ku, Y. T. Yeh and
C. H. Wu, J. Chromatogr., A, 2009, 1216, 6377–6381.
79 M. Anpo, H. Yamashita, Y. Ichihashi, Y. Fujii and
M. Honda, J. Phys. Chem. B, 1997, 101, 2632–2636.
80 K. Ikeue, H. Yamashita, M. Anpo and T. Takewaki, J. Phys.
Chem. B, 2001, 105, 8350–8355.
81 Y. Shioya, K. Ikeue, M. Ogawa and M. Anpo, Appl. Catal., A,
2003, 254, 251–259.
82 S. C. Yan, S. X. Ouyang, J. Gao, M. Yang, J. Y. Feng, X. X. Fan,
L. J. Wan, Z. S. Li, J. H. Ye and Y. Zhou, Angew. Chem., 2010,
122, 6544–6548.
83 S. C. Yan, H. Yu, N. Y. Wang, Z. S. Li and Z. G. Zou, Chem.
Commun., 2012, 48, 1048–1050.
84 P. Li, S. Ouyang, G. Xi, T. Kako and J. Ye, J. Phys. Chem. C,
2012, 116, 7621–7628.
85 G. Xi, S. Ouyang, P. Li, J. Ye, Q. Ma, N. Su, H. Bai and
C. Wang, Angew. Chem., Int. Ed., 2012, 51, 2395–2399.
86 N. Zhang, S. Ouyang, P. Li, Y. Zhang, G. Xi, T. Kako and
J. Ye, Chem. Commun., 2011, 47, 2041–2043.
87 L. Yuliati, H. Itoh and H. Yoshida, Chem. Phys. Lett., 2008,
452, 178–182.
88 L. Yuliati and H. Yoshida, Chem. Soc. Rev., 2008, 37, 1592–1602.
89 J. Fan, E. Liu, L. Tian, X. Hu, Q. He and T. Sun, J. Environ.
Eng., 2011, 137, 171–176.
90 M. Halmann, M. Ulman and B. Aurian-Blajeni, Sol. Energy,
1983, 31, 429–432.
91 Z. Y. Wang, H. C. Chou, J. C. S. Wu, D. P. Tsai and G. Mul,
Appl. Catal., A, 2010, 380, 172–177.
92 P.-Y. Liou, S.-C. Chen, J. C. S. Wu, D. Liu, S. Mackintosh,
M. Maroto-Valer and R. Linforth, Energy Environ. Sci.,
2011, 4, 1487–1494.
93 E. E. Barton, D. M. Rampulla and A. B. Bocarsly, J. Am.
Chem. Soc., 2008, 130, 6342–6344.
94 P. W. Pan and Y. W. Chen, Catal. Commun., 2007, 8, 1546–1549.
95 W. Hou, W. H. Hung, P. Pavaskar, A. Goeppert, M. Aykol
and S. B. Cronin, ACS Catal., 2011, 1, 929–936.
96 M. Ulman, A. Tinnemans, A. Mackor, B. Aurian-Blajeni and
M. Halmann, Int. J. Sol. Energy, 1982, 1, 213–222.
97 M. Halmann, Nature, 1979, 275, 115–116.
98 M. Halmann, V. Katzir, E. Borgarello and J. Kiwi, Sol. Energy
Mater., 1984, 10, 85–91.
99 S. Kaneco, Y. Shimizu, K. Ohta and T. Mizuno, J. Photochem.
Photobiol., A, 1998, 115, 223–226.
100 X. Li, H. Liu, D. Luo, J. Li, Y. Huang, H. Li, Y. Fang, Y. Xu
and L. Zhu, Chem. Eng. J., 2012, 180, 151–158.
101 Q. D. Truong, T. H. Le, J.-Y. Liu, C.-C. Chung and Y.-C. Ling,
Appl. Catal., A, 2012, 437–438, 28–35.
102 Q. D. Truong, J.-Y. Liu, C.-C. Chung and Y.-C. Ling, Catal.
Commun., 2012, 19, 85–89.
103 I. Tseng, W. C. Chang and J. Wu, Appl. Catal., B, 2002, 37,
37–48.
104 I. Tseng, J. Wu and H. Y. Chou, J. Catal., 2004, 221, 432–
440.
105 T. V. Nguyen and J. C. S. Wu, Sol. Energy Mater. Sol. Cells,
2008, 92, 864–872.
This journal is ª The Royal Society of Chemistry 2013

Minireview
106 S. Qin, F. Xin, Y. Liu, X. Yin and W. Ma, J. Colloid Interface
Sci., 2011, 356, 257–261.
Published on 20 December 2012. Downloaded by Indian Institute of Science Education and Research Mohali on 2/21/2024 9:49:04 PM.
107 S. Matsuoka, K. Yamamoto, T. Ogata, M. Kusaba,
N. Nakashima, E. Fujita and S. Yanagida, J. Am. Chem.
Soc., 1993, 115, 601–609.
108 K. Tanaka and J. Fritz, J. Chromatogr., A, 1986, 361, 151–160.
109 O. Ishitani, C. Inoue, Y. Suzuki and T. Ibusuki, J. Photochem.
Photobiol., A, 1993, 72, 269–271.
110 K. Tanaka, T. Matsui and T. Tanaka, J. Am. Chem. Soc., 1989,
111, 3765–3767.
111 X. V. Zhang, S. T. Martin, C. M. Friend, M. A. A. Schoonen and
H. D. Holland, J. Am. Chem. Soc., 2004, 126, 11247–11253.
112 S. Sato, T. Arai, T. Morikawa, K. Uemura, T. M. Suzuki,
H. Tanaka and T. Kajino, J. Am. Chem. Soc., 2011, 133,
15240–15243.
113 S. Yanagida, M. Kanemoto, K. Ishihara, Y. Wada, T. Sakata
and H. Mori, Bull. Chem. Soc. Jpn., 1997, 70, 2063–2070.
114 B. Eggins, J. Irvine, E. Murphy and J. Grimshaw, J. Chem.
Soc., Chem. Commun., 1988, 1123–1124.
115 B. R. Eggins, P. K. J. Robertson, E. P. Murphy, E. Woods and
J. T. S. Irvine, J. Photochem. Photobiol., A, 1998, 118, 31–40.
This journal is ª The Royal Society of Chemistry 2013
View Article Online
Analytical Methods
116 J. Irvine, B. Eggins and J. Grimshaw, Sol. Energy, 1990, 45,
27–33.
117 L. Cao, S. Sahu, P. Anilkumar, C. E. Bunker, J. Xu,
K. A. S. Fernando, P. Wang, E. A. Guliants, K. N. Tackett
and Y.-P. Sun, J. Am. Chem. Soc., 2011, 133, 4754–4757.
118 C. Kutal, M. A. Weber, G. Ferraudi and D. Geiger,
Organometallics, 1985, 4, 2161–2166.
119 T. V. Nguyen, J. C. S. Wu and C. H. Chiou, Catal. Commun.,
2008, 9, 2073–2076.
120 T. Nash, Biochem. J., 1953, 55, 416.
121 U.S. EPA method 8315A, Determination of Carbonyl
Compounds by HPLC, 1994.
122 W. M. Grant, Anal. Chem., 1948, 20, 267–269.
123 J. S. Kiel, S. L. Morgan and R. K. Abramson, J. Chromatogr.,
A, 1985, 320, 313–323.
124 H. Claessens, M. Van Straten and J. Kirkland, J. Chromatogr.,
A, 1996, 728, 259–270.
125 D. E. Jordan, Anal. Chim. Acta, 1980, 113, 189–194.
126 W.-N. Wang, W.-J. An, B. Ramalingam, S. Mukherjee,
D. M. Niedzwiedzki, S. Gangopadhyay and P. Biswas,
J. Am. Chem. Soc., 2012, 134, 11276–11281.
Anal. Methods, 2013, 5, 1086–1097 | 1097