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Recent advances in VOC elimination by catalytic oxidation technology

onto various nanoparticles catalysts: a critical review

Yunlong Guo (Investigation) (Formal analysis) (Writing - original

draft), Meicheng Wen (Writing - review and editing), Guiying Li
(Writing - review and editing), Taicheng An (Conceptualization)
(Supervision) (Writing - review and editing)

PII: S0926-3373(20)30862-6
DOI: https://doi.org/10.1016/j.apcatb.2020.119447
Reference: APCATB 119447

To appear in: Applied Catalysis B: Environmental

Received Date: 12 June 2020

Revised Date: 10 August 2020
Accepted Date: 13 August 2020

Please cite this article as: Guo Y, Wen M, Li G, An T, Recent advances in VOC elimination by
catalytic oxidation technology onto various nanoparticles catalysts: a critical review, Applied
Catalysis B: Environmental (2020), doi: https://doi.org/10.1016/j.apcatb.2020.119447

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Recent advances in VOC elimination by catalytic oxidation
technology onto various nanoparticles catalysts: a critical review

Yunlong Guo, Meicheng Wen, Guiying Li, Taicheng An*

Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Guangzhou

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Key Laboratory of Environmental Catalysis and Pollution Control, School of Environmental

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Science and Engineering, Institute of Environmental Health and Pollution Control, Guangdong

University of Technology, Guangzhou 510006, China

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Corresponding author:

Prof. Taicheng An, Tel: 86-20-39322298, E-mail: antc99@gdut.edu.cn;

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Graphical abstract

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Highlights
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 Selection of various nanoparticle catalysts is analyzed on the basis of VOC sorts
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 The catalyst performance metric is unified for comparison among different studies

 VOC oxidation mechanisms based on experimental and theoretical data are summarized
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 Integrating thermocatalysis with photocatalysis for VOC elimination is emphasized

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ABSTRACT

Volatile organic compounds (VOCs) with the properties of volatility, toxicity and diffusivity

pose a serious threat to human health and eco-environment. Catalytic oxidation technology has

been considered as a highly efficient option for the treatment of VOCs. This review

systematically summarizes the recent processes and advances on catalytic elimination of VOCs

over nanoparticles catalysts. Firstly, catalytic performances of catalysts for VOC degradation

are evaluated and compared on the basis of unified performance metrics. Secondly, catalytic

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mechanisms of VOC oxidation, based on experimental and theoretical studies, are

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systematically introduced. Then, catalytic reactors employed in VOC elimination processes are

summarized. In particular, photothermocatalysis by integrating (thermo)catalysis with

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photocatalysis is also elucidated. Lastly, the perspectives to the scientific issues and challenges
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faced, as well as the future outlooks are proposed. Collectively, this review will provide

theoretical and experimental foundation for rational fabrication and application of nanoparticles
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catalysts toward VOC elimination in future.

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Keywords: The elimination of VOCs; Nanoparticles catalysts; Performance evaluation;

Catalytic oxidation mechanism; Photothermocatalysis

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1. Introduction
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At present, air pollution purification has received extensive research and becomes

one of the public concerns. Volatile organic compounds (VOCs) are of dominant

pollutants with the boiling points below 260°C at the condition of room temperature [1].

VOCs with the characteristics of easy diffusivity, toxicity and volatility released into

environmental matrixes are regarded as a critical factor to air pollution and give rise to
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a serious damage to the eco-environments and human health [2,3]. VOCs are emitted

from a large variety of sources, including outdoor sources (industrial processes and

transportation) and indoor sources (household products, such as construction materials,

consumer products, furniture, combustion byproducts and cooking) [4,5]. Due to the

harmful characteristics of VOCs, the emissions of VOCs into atmospheric environment

are controlled by strict regulations in recent years. China has promised to reduce the

VOC emissions by 10% during the Chinese 13th Five-Year Plan (2016-2020), in

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comparison with those of 2015 [1]. Besides, according to the 2006 Goteborg protocol,

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the VOC emissions in the European Union (EU) countries should be reduced by half by

the end of 2020, compared with that of 2000 [6,7]. Hence, the efficient purification of
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VOCs is of significant importance and has gave rise to numerous attentions in recent
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years. Some review papers on VOC elimination were published in recent years. For

example, in 2018, Du et al. [8] reported on the catalytic elimination of chloroaromatics

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from the perspectives of flue gas. He et al. [3] published a review in 2019 which
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demonstrated the developments of heterogeneous catalysts toward VOC catalytic

oxidation. Also, in 2019, Vikrant et al. [9] presented an overview of

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photothermocatalytic systems toward benzene oxidation. In 2020, Lee and co-workers

[10] documented an overview of VOC elimination by using catalysis and catalytic hybrid
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technologies.

Various VOC purification methods have been explored, including adsorption,

condensation, membrane separation, biological degradation, non-thermal plasma

oxidation, photocatalytic decomposition, thermal incineration as well as (thermo)

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catalytic oxidation [11-15]. The words of “thermocatalytic” and “thermocatalysis” are

abbreviated as “catalytic” and “catalysis” in this paper. Among those methods, catalytic

oxidation technology is regarded as an efficient method due to its high economic feasibility,

low cost and low levels of the generation of secondary pollutants [11,16-19], and it can be

operated at a lower temperature with the controlled selectivity of the by-products. Of the

catalytic oxidation methods, the VOC reaction rate is highly depended on the catalytic

nanomaterials during the degradation process. Therefore, the rational design and

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fabrication of highly active and cost-effective catalytic nanomaterials for the elimination

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of VOCs is critically important in realistic applications [20,21].

Currently, the catalytic nanomaterials employed for VOC degradation can be

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mainly divided into two types: noble metal supported catalysts and metal oxide-based
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catalysts [21]. Generally, the noble metal supported catalysts are widely used owing to

their good catalytic activity and high durability in spite of the expensive costs [22,23]. In
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contrast, metal oxide-based catalysts are deemed as the promising candidates owing to
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the advantages of comparatively high catalytic performance, low cost and strong

resistance to poisoning [24,25,26]. However, the design and fabrication of efficient catalyst
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for the catalytic VOC oxidation are still highly challengeable, because of the large sorts of

VOCs and the complicated characteristics of VOC mixtures encountered in practice [7,27,28].
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The catalytic activity of noble metal supported catalysts and metal oxide-based catalysts for

VOC oxidation is mainly depended on the intrinsic properties, morphologies of supports and

active site [1,29]. Generally speaking, the supports of catalysts can be divided into two types

[30,31]: one is the active support, in which itself has certain catalytic activity toward the

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oxidation of VOCs, such as CeO2, Co3O4, MnOx, etc. [23,32-34]; another is the inert support,

in which itself does not shown any catalytic activity for the abatement of VOCs, such as

C, CaCO3, Al2O3, eggshell, diatomite, molecular sieves, ceramics, etc. [11,35-37]. The

role of such inert support is used to provide the surface and pore structures for uniformly

dispersing the active components.

In addition to this, the catalytic reaction conditions, such as VOC sorts and

concentration, gas flow rate, weight of catalyst as well as space velocity, have also play

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an important role in the catalytic performances of the catalysts during VOC degradation

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processes [3]. Among these, the selection of the catalyst is highly depended on the sorts of

VOCs. For instance, noble metal supported catalysts usually have superior catalytic activity and
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stability toward the combustion of aliphatic hydrocarbons, oxygenated VOCs and aromatics.
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However, those catalysts are not suitable for the catalytic oxidation of Cl- and S-containing

VOCs, owning to the catalyst poisoning caused by Cl-, S-intermediates [1,3]. Accordingly,
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metal oxide-based catalysts with the properties of excellent resistance to Cl-, S-

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intermediates can be regarded as an alternative to noble metal supported catalysts toward

Cl- and S-containing VOC degradation [1,3]. Therefore, for the purpose of rational design and
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selection of catalytic nanomaterials for various VOC elimination, a deeper understanding of

oxidation mechanisms during the degradation process should be systematically conducted.

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Catalytic oxidation kinetics, in situ online analysis and theoretical simulation

calculations are useful techniques to explore the mechanisms of VOC oxidation over

different catalysts during the degradation process. Regarding to oxidation kinetic

analysis, three kinetic mechanisms are proposed, which are Eley-Rideal (E-R), Langmuir-

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Hinshelwood (L-H) and Mars-van Krevelen (MVK) mechanisms [1]. By exploring the types

of oxygen species, oxygen vacancies and adsorbed sites of VOCs on catalyst surface,

the reactive path of VOC oxidation over catalytic nanomaterials can be elucidated by

conducting the oxidation kinetics. In addition, the in situ online techniques are effective

tools for the detection and identification of the existed species along with the VOC

degradation process, and thus the elimination mechanisms including the active sites of

catalysts, migration and transformation of the intermediate species, reactive pathways can be

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speculated by combining other characterizations [38,39]. Among in situ online techniques, in

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situ FTIR/DRIFTS can be employed not only for detecting the intermediate species generated

during VOC oxidation process, but also for clarifying the active sites of the catalytic nanomaterials
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[38]. As for MS-based techniques, such as GC-MS, SIFT-MS, PTR-TOF-MS and TOF-SIMS, the
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intermediate species during VOC oxidation can be qualitatively identified by measuring the m/z

of the generated organic compounds [39]. As a fundamental research, theoretical simulation

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calculations based on the interactions between catalysts and VOC molecules can not only
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elucidate the experimental data obtained, but also reveal the intrinsic factors for the enhanced

performance of catalyst toward VOC oxidation. Hence, theoretical simulation calculations are
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an ideal approach for the explanation of catalytic mechanism of VOC degradation.

Apart from the researches of catalyst and elimination mechanisms toward VOC
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oxidation, the catalytic reactors used in the combustion processes also play an important

role [40-41]. Among catalytic reactors, fixed-bed reactor and fluidized-bed reactor are

the most used two kinds of reactors in catalytic VOC combustion. In the case of fixed-

bed reactors, they are grouped as continuous-flow fixed-bed reactors and membrane

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reactors, and the differences are the catalytic materials used in the reactors, which are

particle-shaped/monolithic catalysts and membrane-based catalysts, respectively [3].

Generally speaking, the majority of the literatures regarding to VOC destruction are

related to fixed-bed microreactors; however, the large-scale reactors are usually adopted

in realistic industrial flue streams, in which the catalysts are normally presented in the

form of monolith or membrane [40-42]. Hence, the applicability of reactors should

depend on the properties of catalysts, the concentration of inlet VOCs and the operation

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conditions in practical applications.

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Although catalytic oxidation technology has plenty of merits for the efficient

elimination of VOCs, in comparison with other traditional removal technologies, high

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reaction temperature is still required for the complete destruction of VOCs.
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Photocatalysis can oxidize low-concentration VOCs at room temperature, nevertheless,

this method has the disadvantages of low destruction efficiency and poor catalytic
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durability, due to the low light utilization efficiency and the coke deposits on the catalyst
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[5,43,44]. Hence, photothermocatalytic oxidation technology by integrating thermocatalysis

with photocatalysis is developed as a promising strategy, due to higher catalytic activity with
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lower reaction temperature, since it can maximize the synergistic effects of thermocatalysis and

photocatalysis at relative low temperature [21,45-47]. A large number of achievements have

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been achieved by employing photothermocatalytic approach in recent years [21,45,48].

Therefore, photothermocatalytic degradation is regarded as a suitable and hopeful technology

for VOC treatment in near future.

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 Recently, there have been few review articles discussing the latest advances of

various catalysts towards VOC catalytic oxidation [3,10]. Nevertheless, those reviews

were mainly focused on the structure-activity relationship of the catalysts toward VOC

degradation, few attentions have been comprehensively and systematically paid on VOC

oxidation mechanism, normalized comparison of catalyst performance as well as

photothermocatalytic elimination. In this review paper, first, by virtue of the detail

investigation and summary, the recent progress and challenge of VOC oxidation

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mechanisms by combining oxidation kinetic mechanisms, in situ online analysis and

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theoretical simulation calculations are systematically clarified. Then, regarding to

performance evaluation metrics of the catalysts toward VOC degradation, much attention is
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payed to the VOC conversion temperatures (e.g., T10%, T50% and T90%) in the previous works,
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which are inappropriate for different catalytic systems owing to the different reaction

parameters. Hence, the reaction rate of VOC oxidation, as a comprehensive and accurate
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performance metrics of catalytic reactions, is applied for the performance evaluation of the
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catalysts, of which the unit is normalized and all the related variables are considered. To the

best of our knowledge, such a performance metric is rarely summarized in previous review
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papers. Finally, photothermocatalytic degradation technology by integrating

thermocatalysis with photocatalysis is also emphasized, in which figure of merit (FoM)

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is demonstrated for the performance comparison of catalytic nanomaterials under batch-

mode photothermocatalytic systems. Also, very few reviews on VOC

photothermocatalytic degradation are presented. In general, this review can be

systematically divided into five sections. (1) Different kinds of VOCs, including

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aromatics, aliphatic hydrocarbons, oxygenated VOCs (OVOCs), halogenated VOCs and

N, S-containing VOCs, are conducted for the catalytic performance evaluation of the

employed nanoparticle catalysts. (2) The studies of VOC oxidation mechanisms on the

basis of catalytic oxidation kinetics, in situ online analysis and theoretical simulation

calculations are discussed in detail. (3) The advantages and disadvantages of different

catalytic reactor used for VOC oxidation are also summarized for possible industrial

application. (4) Photothermocatalytic degradation technology is also introduced and

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discussed. (5) The challenges and the perspectives of the VOC elimination are reviewed

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and summarized. Collectively, it is demonstrated that this review will inspire ongoing

efforts to rational design of nanoparticles catalysts toward efficient catalytic oxidation

of various VOCs in practical applications.

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2. VOC sorts and their catalytic elimination
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VOCs are not only toxic, volatile and carcinogenic, but also involve in the variation of

climate as well as the formation of ground-level ozone, aerosol and smog [49]. Hence, the
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development of catalytic nanomaterials for efficient destruction of VOCs is urgently needed.

More than 300 groups of VOCs are released into the atmospheric environment, which can be
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divided into five categories: aromatics, aliphatic hydrocarbons, oxygenated VOCs, halogenated
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VOCs and N, S-containing VOCs [1]. It is generally accepted that the nature of different kinds

of VOCs, such as chemical structures, electronic environments and the physicochemical

properties, are different [3]. Therefore, the destruction of different types of VOCs should be

taken into consideration by employing different catalysts. Generally speaking, the acid/base

properties of supports, the strategy of catalyst preparation method, the nature of active sites as
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well as the catalytic reaction conditions all play a critical role in elimination efficiency, activity,

durability, selectivity and resistance of Cl, S poisoning of various nanoparticles catalysts toward

VOC catalytic destruction [8,16].

In the performance evaluation metrics of the catalysts toward VOC degradation, the

conversion of VOCs (XVOCs, %) is the most commonly used evaluation standard. With regard

to the VOC conversion, the temperatures required for 10%, 50% and 90% VOC conversions

(T10%, T50% and T90%) are generally used performance evaluation metrics of catalysts [27].

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Nevertheless, these metrics are only comparable and suitable for the catalysts applied under the

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same catalytic system, in which the catalytic reaction parameters are all the same. Therefore, a

comprehensive performance evaluation metric of various catalysts operating at different

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catalytic systems should be introduced, of which the related variables of catalytic reaction are
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considered [50,51]. Hence, the reaction rate of VOC oxidation is put forward and the unit is

normalized, and the equation is presented as follows:

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CVOCs*XVOCs*Vgas
Reaction rate = (mol gcat-1 s-1) (1)
m

Where CVOCs is initial concentration of VOCs, Vgas (mol s-1) is the total molar flow rate, and m
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(g) is the mass amount of the catalyst. The molar volume of gas used in the equation is 24.5 L
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mol-1. To the best of our knowledge, such a performance metric is rarely calculated and

summarized among various types of catalysts for VOC abatement in previous review papers.
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2.1. Aromatics elimination

Aromatic hydrocarbons are a class of VOCs commonly generated from industrial process,

which are regarded as a serious threat to human health and atmospheric environment [52]. Among

the aromatics, benzene, toluene, ethylbenzene and xylene (BTEX) can be regarded as the most

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common aromatic VOCs, which are very toxic and carcinogenic. Aromatic hydrocarbons with the

characteristics of benzene-ring structure are stable and require high temperature to be destructed

[38]. The catalytic oxidation of aromatics has been studied by lots of researchers, and as is well

known, the efficiency of catalytic oxidation highly depends on the elimination performance of

catalysts. Among various catalysts, noble metal (Pd, Pt, Au, Ru and Ag) nanoparticles supported

catalysts and metal oxide-based (Co, Mn, Ce, Al, La, Zn, Ni and Cu) catalysts have been carefully

explored and investigated toward the catalytic degradation of aromatics (Table 1). It is worth

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noting that the reaction rates in Table 1 are calculated according to Eq. 1 in this review. The

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calculation parameters are normalized and unified for the purpose of comparison, in which the

reaction temperatures of VOC degradation are all set to be 190oC, and thus the corresponding
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conversions of VOCs can be obtained by the figures of temperature-conversion. From Table 1, the
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majority of reaction rates of VOCs over noble metal supported catalysts are higher than those of

metal oxide-based catalysts, indicating the excellent catalytic performance of noble metal
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supported catalysts for aromatics catalytic oxidation. Among the noble metals, Pt- and Pd- based
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catalysts are most widely used in the oxidation of aromatics owning to their excellent catalytic

activity and stability, which can be ascribed to the nature of the noble metals, weak noble metal-O
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bonds as well as the strong interactions between noble metal and support [22,50]. The highest

reaction rate (1.016 μmol gcat-1 s-1) was achieved for benzene-based VOC degradation over
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1.0Pt/Al2O3, exhibiting good catalytic performance of Pt-based catalytic nanomaterials (Table 1).

For metal oxide-based catalysts, Co-, Mn-, Ce-based catalysts are the most commonly used and

demonstrate superior catalytic activity, and the reasons can be assigned to the easy transformation

of metal valence, low-temperature reducibility, abundant oxygen species, large Brunner-Emmet-

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Teller (BET) specific surface area [10]. Among these catalysts, ZnCo2O4 demonstrated excellent

degradation efficiency for aromatics oxidation, in which the reaction rate could reach up to

0.188 μmol gcat-1 s-1 (Table 1), showing that Co-based catalysts can be regarded as an ideal

catalytic nanomaterial for VOC degradation [38].

The catalytic performance of noble metal supported catalysts is not only closely related to

the noble metals, but also relevant to the properties of the support. The acid-base property of

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the support usually has an important influence on catalytic performance of catalyst toward VOC

combustion. For example, Hao et al. [81] prepared a series of molecular sieves supported Pd

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catalysts for catalytic combustion of benzene, toluene and ethyl acetate. The catalytic
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performance decreased in the sequence of Pd/Beta > Pd/ZSM-5 > Pd/SBA-15 > Pd/MCM-48

> Pd/MCM-41. The reason can be ascribed to the higher acidity of the support and thus result
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in strong and large quantity of acid sites of the catalysts, which are beneficial for the active sites
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dispersion and CO2 desorption from the catalysts. Although Pd/ZSM-5 had inferior catalytic

performance than that of Pd/Beta, it demonstrated a better catalytic durability even after 72 h
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of on-stream elimination, which was more appropriate for practical application. Nevertheless,

Okumura et al. [82] reported that Pd supported on metal oxide-based supports as catalysts were
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used for toluene oxidation. It is demonstrated that acid-base properties of the metal oxides are
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responsible for the stabilization of metal Pd, and the results showed that Pd/ZrO2 with weaker

acidity had highest catalytic activity. Besides, similar observations could be also expressed by

He and co-workers for the destruction of toluene over the Pd/ZSM-5 catalyst based on the

acidity of the support [83]. Collectively, the acid-base properties of support have an important

influence on the catalytic performance of the supported catalysts.

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 In some cases, the alkali metal doping can be regarded as an effective candidate to improve

the catalytic performance of the catalyst due to the electronic promotion effects for those

catalysts. For example, Chen et al. [84] synthesized a series of alkali metal elements (e.g., H, Na,

K and Cs) doped Pt/ZSM-5 catalyst, and found that the doping of alkali metal onto mesoporous

ZSM-5 support could greatly improve the catalytic activity of Pt/ZSM-5 for toluene oxidation as

compared with the undoped one. The Pt/KZSM-5 demonstrated superior catalytic performance

than other doped catalysts. Particularly, Pt/KZSM-5 could perform constantly for 50 h of on-

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stream reaction and demonstrated negligible inhibition of H2O and CO2. Similar result was also

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obtained by the same group, in which doping K+ onto the support of Beta-SDS could enhance the

catalytic toluene oxidation over the catalyst [85]. The Pt/KBeta-SDS conducted a T98% value as
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low as 150°C (60,000 mL g-1 h-1) and the corresponding reaction rate at this temperature was
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calculated to be 0.667 μmol g-1 s-1, which was higher than that of undoped one. The enhanced

catalytic performance of Pt/KBeta-SDS can be ascribed to the formation of more Pt0 species
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and the adsorption of toluene because of the higher K+ content. In general, the doping of alkali
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metals can both enhance the adsorption of VOCs and change the proportion of noble metal

valence state, and finally promoting the VOC catalytic activity of the catalysts. The above
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characteristics of these catalysts are very beneficial for practical VOC elimination in the future.

Although noble metal supported catalysts have excellent catalytic activity for VOC oxidation,
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the cost of such catalysts is expensive owing to the scarcity of noble metals. Transition metal oxide

catalysts are much cheaper and more abundant than noble metals, and thus have attracted

considerable attentions in recent years [1]. Taking CeO2 catalyst as an example, three CeO2

catalysts with different morphologies (rods, cubes and particles) were prepared and evaluated for

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o-xylene oxidation [70], in which the T90% were 239°C, 242°C and 272°C (60,000 mL g-1 h-1),

respectively. The results showed that the CeO2 with the morphology of rods had the best

catalytic performance owing to the (111) and (100) facets exposed, and the specific reaction

rate and reaction rate over CeO2 rods was 1.48×10-3 μmol s-1 m-2 and 0.116 μmol g-1 s-1,

respectively (both measured at 210°C), which were both higher than that of CeO2 particles and

CeO2 cubes. In addition to pristine metal oxide catalysts, the doped or mixed metal oxide

catalysts are also studied by numerous researchers [86]. For example, Liao et al. [87]

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investigated that doping Ce onto the MnOx can enhance the toluene catalytic activity and stability

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of the parent MnOx catalysts, in which the reaction rates for toluene oxidation over Mn0.85Ce0.15,

MnOx and CeO2 were calculated to be 0.160, 0.091 and 0.062 μmol g-1 s-1, respectively (the
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temperature of 190°C and SV of 32,000 mL g-1 h-1). The enhanced performance of Mn0.85Ce0.15
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was mainly due to the generation of a mixed Mn-Ce oxide phase, resulting in an increase of Mn4+

species and oxygen vacancies. In addition, Carabineiro et al. [88] evaluated the doping of Ce or
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La onto cobalt oxides as a catalyst for the oxidation of toluene. It was found that Ce-Co and La-
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Co catalysts had better catalytic activity than single Co3O4, CeO2 or La2O3 catalysts. The T90%

over Ce-Co and La-Co were 241°C and 283°C (600,000 mL g-1 h-1) and the reaction rates were
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1.629 and 0.362 μmol g-1 s-1, respectively (reaction temperature of 242°C). The high catalytic

performance of Ce-Co catalyst could be ascribed to the improved interactions between Ce and Co,
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leading to high dispersion of the active oxide phases. Collectively, these investigations are

fundamental for rationally designing of high-performance catalysts for VOC elimination.

2.2. Aliphatic hydrocarbons elimination

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 Aliphatic hydrocarbons are normally emitted from natural sources or petroleum, which are

composed of the elements of carbon and hydrogen [1]. According to the degree of saturation of C-

H bonds, it can be divided into saturated alkanes (methane, ethane, propane, hexane, pentane, etc.)

and unsaturated alkenes/alkynes (ethylene, propene, butene, acetylene) [3]. Aliphatic

hydrocarbons have adverse effects on human health and environment, and could further produce

OVOCs and aerosols through a series of photochemical reactions in atmospheric environments

[13]. Hence, the catalytic destruction of these VOCs is urgently needed in our actual living

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environment. To date, a great variety of catalysts including noble metal nanoparticles supported

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catalysts (Pd-, Au-, Rh-, or Pt-based catalysts), transition metal (Mn, Co, Cu, Cr, Ce and Ni) oxides

and perovskites (LaCoO3, LaxSr1-xMnO3) are employed for the catalytic oxidation of such VOCs

[1,7].
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Generally, supported Pt- and Pd- based catalysts are well known to be active for the oxidation

of hydrocarbons because of their excellent low-temperature catalytic activities [89,90]. Surface

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valence, mean particle size and dispersion of the noble metal on the catalysts have a crucial
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influence on the elimination of aliphatic hydrocarbons. Taking Pt/Al2O3 catalyst as an example,

Haneda et al. [91] synthesized a series of Pt/Al2O3 catalysts with different Pt dispersion and
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evaluated their catalytic activity for propene oxidation. Among this study, it was found that

with the increase of Pt dispersion, the catalytic activity was also enhanced. 1.0Pt/Al2O3 with
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the dispersion of 0.81 showed not only better degradation efficiency (T90% of 177°C, 100,000

mL g-1 h-1), but also higher reaction rate (0.667 μmol g-1 s-1, reaction temperature of 195oC).

Besides, Aznarez et al. [92] synthesized Pd- and Pt- Al-PILC catalysts, and 1.0Pd/Al-PILC

demonstrated better catalytic activity for propene oxidation, in which T90% were approximately

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260°C (20,000 h-1), compared to 350°C of 1.0Pt/Al-PILC. The reaction rates for propene

oxidation over Pd- and Pt-based catalysts were 1.31 and 0.56 μmol g-1 s-1 (reaction temperature

of 195°C), also indicating the excellent degradation efficiency of 1.0Pd/Al-PILC.

Noble metal supported catalysts used for the oxidation of aliphatic VOCs usually have the

disadvantages of easy deactivation due to high reaction temperature and high loadings of noble

metal. Thus, the introduction of non-noble metal into noble metal supported catalysts are being an

alternative in recent years. For example, Xie et al. [90] synthesized a series of Pd@Co supported-

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CeO2 catalysts for the catalytic oxidation of methane, in which the active phase is presented in the

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form of core-shell structure (Pd@Co). The Co3.5Pd/CeO2 catalyst showed superior catalytic

performance, as compared with other single-metal and alloyed catalysts (Fig. 1a). This catalyst
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conducted T90% of 480°C (40,000 mL g-1 h-1) and reaction rate of 6.888 μmol g-1 s-1 (reaction
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temperature of 440°C). In addition, this catalyst was catalytically stable for methane oxidation in

the temperature range of 400°C-800°C, as compared with that of Pd/CeO2 (Fig. 1b).
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In contrast to some noble metal supported catalysts, metal oxide catalysts also displayed
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relative high catalytic performance with lower cost and excellent thermal stability [51]. The

metal valence, BET specific surface area, porous structure, dispersion of the active phase,
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exposure of specific face and oxygen species have a decisive role in the oxidation of
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hydrocarbons over these kinds of catalysts [3,51]. For example, Co3O4-CeO2 catalysts with the

Co/Ce ratio of 30 demonstrated high catalytic performance for the oxidation of propene,

compared to the catalysts with other Co/Ce ratios, in which the reaction rate was 0.057 μmol g-

1 -1
s (calculated at 180°C) and T90% was reduced to 225°C (36,000 mL g-1 h-1) [93]. The superior

activity of Co3O4-CeO2 was ascribed to both high BET specific surface area as well as increased
17
dispersion of Co3O4 in coupled catalysts. Besides, Wang et al. [94] synthesized one mesoporous

LaCoO3 catalyst using nanocasting method, and then applied in the catalytic combustion of

methane. The catalytic performance of this mesoporous LaCoO3 were much higher than that of

the bulk LaCoO3 prepared with the citrate method, in which the reaction rates were calculated to

be 1.850 and 0.218 μmol g-1 s-1, respectively (the calculated temperature of 440°C). The high

catalytic performance of mesoporous LaCoO3 could be ascribed to high porosity and large BET

specific surface area.

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2.3. OVOC elimination

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Oxygenated VOCs, such as alcohols (methanol and ethanol), aldehydes (formaldehyde),

-p
ketones and ethers, are mainly originated from the oxidation of hydrocarbons, industrial waste

streams and natural behaviors. It is worth noting that the atmospheric photooxidation of
re
hydrocarbons is one of the major sources of OVOCs, and these species contributed seriously to
lP

the generation of aerosol and ozone. For example, formaldehyde (HCHO) that is regarded as a

typical OVOC commonly present at indoor room is seriously harmful to human health; the
na

maximum acceptable HCHO concentration is as low as 0.1 ppb in 30 min [14]. To date,

numerous reports are contributed to the destruction of OVOCs at lower or even room
ur

temperature. Among the catalysts used, noble metal (Pt, Au, Rh, Ag and Pd) supported catalysts
Jo

are especially emphasized in the elimination of OVOCs due to their complete conversion at

very lower temperature, in contrast to transition metal oxides (Co, Ni, Mn, Cr) catalysts [95-

98].

From the perspectives of dynamics, the adsorption and activation of OVOCs, such as HCHO,

is the key step for destructing these pollutants, in which -OH groups existed on the surface of

18
catalysts are demonstrated to play a significant role, and one of the effective methods to increase

the concentration of -OH groups is to add alkali metal salts onto the supported catalysts [99-101].

Doping alkali metal ions (Li+, K+ and Na+) onto TiO2-supported noble metal catalysts can greatly

enhance the performance of catalysts toward the HCHO oxidation at room temperature [102]. For

example, Zhang et al. [97] synthesized a series of Na-Pt/TiO2 catalysts, and found that Na ions

addition had an obvious enhancement on the catalytic activity of Na-Pt/TiO2, in which complete

conversion of HCHO could be achieved over Na-doped catalysts at room temperature (reaction

of
conditions: HCHO concentration of 600 ppm and GHSV of 120,000 h-1). The reaction rates for

ro
HCHO oxidation over 2.0Na-1.0Pt/TiO2, 1.0Na-1.0Pt/TiO2 and 1.0Pt/TiO2 were calculated to be

0.816, 0.784 and 0.155 μmol g-1 s-1, respectively (reaction temperature of 15°C). The higher
-p
degradation efficiency of 2.0Na-1.0Pt/TiO2 could be ascribed to the OH activation by alkali-metal
re
ion addition and the reaction between formate species and surface OH. In addition, the acid/base

properties of the support of noble metal supported catalyst usually have a significant influence on
lP

the dispersion of noble metals in catalysts. Taking zeolite support as an example, a series of noble
na

metals-supported (Pd/HY, Pd/NaY and Pd/Al2O3) catalysts were synthesized comparably for the

catalytic oxidation of methanol [96], and it demonstrated that Pd/HY catalyst has the highest
ur

catalytic performance, which could be attributed to higher acidity of HY support together with

high dispersion of Pd NPs. The T90% values of 1.5Pd/Al2O3, 1.5Pd/NaY and 1.5Pd/HY were
Jo

209, 145°C and 120°C, respectively (GHSV of 24,000 mL g-1 h-1). Also, higher reaction rate

over 1.5Pd/HY was calculated to be 9.796 μmol g-1 s-1 (reaction temperature of 120°C).

Although the complete catalytic oxidation of VOCs into H2O and CO2 is an efficient method for

VOC control, it has some disadvantages, such as high cost, the waste of resources and the

19
increasement of CO2 emissions. At present, selective catalytic oxidation may be a novel and

economic method, since it can convert VOCs into other useful products. For example, Zhang et

al. [103] reported that Au/α-Fe2O3 nanosheets were employed for selective catalytic oxidation of

isopropanol to acetone, in which acetone selectivity and yield were 99% and 95% at 220°C,

respectively.

Although noble metal supported catalysts have excellent catalytic activity for OVOC

elimination, the cost of those catalysts is still expensive. Transition metal oxide catalysts are much

of
cheaper and more abundant, and thus can be regarded as an alternative toward the oxidation of

ro
some sorts of OVOCs. Xia et al. [104] prepared 3D ordered mesoporous (3DOM) Co3O4 and

nonporous Co3O4 for the oxidation of methanol, and the T50% over 3DOM Co3O4 and nonporous
-p
Co3O4 were 105°C and 142°C, respectively (20,000 mL g−1 h−1). Besides, the reaction rates were
re
calculated to be 0.206 and 0.109 μmol g-1 s-1, respectively (reaction temperature of 140°C). The

high degradation efficiency of 3DOM Co3O4 could be assigned to 3DOM structure, super
lP

reducibility and high specific surface area. Until now, the doping of alkali metals onto the transition
na

metal oxides has been systematically studied for the enhancement of catalytic oxidation of HCHO.

Taking MnO2 as an example, Xu et al. [105] prepared the K-doped hollandite MnO2 (K1/HMO)
ur

as catalysts toward the oxidation of HCHO. They concluded that the surface isolated K atoms with

hybridized d-sp orbitals can obviously improve the activation ability of oxygen, thus promoting
Jo

the catalytic performance of HCHO oxidation. K1/HMO had higher catalytic activity for HCHO

oxidation, and the reaction rate over K1/HMO was 2.041 μmol g-1 s-1, 40% higher than that of

HMO at the same reaction temperature of 120°C. Nevertheless, the excessive doping onto metal

oxides may lead to the decrease of catalytic activity. For example, Rong et al. [106] incorporated

20
K into birnessite MnO2 for the catalytic oxidation of HCHO. The catalytic activity of catalyst

was originally increased with the amount of K, then decreased with the excessive doping of K

into MnO2. The 1K/MnO2 showed highest catalytic activity with T90% of 82°C (90,000 mL g−1

h−1) and corresponding reaction rate of 0.092 μmol g-1 s-1. The reason was that the oxygen

species near the K elements became less mobile when the excessive K was doped, resulting in

the decrease of catalytic activity. In general, the amount of K doping should be optimized for

MnO2-based catalyst toward the excellent oxidation of HCHO.

of
2.4. Halogenated VOC elimination

ro
Halogenated VOCs, such as trichloromethane, dichlorobenzene, trichloroethylene,

-p
tetrachloromethane and chlorobenzene, are all hazardous and toxic substances to atmospheric

environments and human health [107]. Besides, the halogenated VOCs containing halogen
re
elements, such as fluorine, chlorine, bromine or iodine, contributes seriously to the generation
lP

of greenhouse gas [108]. The halogenated VOCs are mainly emitted from medicines, printing,

rubber and pesticides [3], and they are also raw materials for the production of insecticides,
na

herbicides, fungicide, paints, adhesives, drug manufacturing, etc. [109]. Among halogenated

VOCs, chlorinated volatile organic compounds (CVOCs) have been frequently selected as model
ur

pollutants owing to their high emission, toxicity and chemical stability [110]. In recent years,
Jo

catalysts for the destruction of halogenated VOCs can be comprised of noble metal supported

catalysts and metal oxide-based catalysts [8,111]. Generally speaking, one difficult point for

catalytic oxidation of CVOCs is the catalyst deactivation poisoned by the chlorine/chloride

products generated during catalytic process [112-114]. Another difficult point is the high

selectivity to HCl rather than other chlorine/polychlorinated byproducts for the oxidation of

21
CVOCs, since some Cl-byproducts are more harmful and toxic, in comparison with the original

pollutants [3]. In general, the catalysts employed for halogenated VOC oxidation should have the

characteristics of excellent catalytic stability and high selectivity to HCl species.

Although transition metal oxide catalysts have lower catalytic activity, they have better

resistance to chlorine poisoning, compared with noble metal supported catalysts [1,8]. Regarding

transition metal oxide-based catalysts, the active phase is usually loaded on the supports to increase

the catalytic performance of catalysts. Ce-, Mn-, Cr-, V-, Co- oxides and their mixed oxides are

of
normally regarded as the active phase, which are supported onto TiO2, ZrO2, Al2O3 and zeolite to

ro
design highly dispersive active catalysts [8]. It is worth noting that polychlorinated byproducts

generated during the catalytic processes are easily polymerized into dioxins, which are more toxic
-p
to human beings and the environments [115]. Besides, the undesired byproducts will cover the
re
active sites of catalysts, resulting in the poisoning and subsequent deactivation of the catalysts.

Therefore, some modified methods, such as the tuning support, the introducing water vapor, the
lP

acid/base treatment, and the addition of dopants can obviously enhance the catalytic stability and
na

increase catalytic selectivity over the catalysts toward CVOC oxidation [8].

For example, Sun et al. [115] synthesized a series of catalysts for chlorobenzene oxidation.
ur

Among these catalysts, Mn0.8Ce0.2O2/H-ZSM-5 exhibited not only better degradation efficiency

(T90% of 230°C, 10,000 h-1), but also higher reaction rate of 0.098 μmol g-1 s-1, far better than other
Jo

kinds of catalysts. The excellent catalyst performance could be ascribed to the synergistic effect

between MnOx and CeO2 as well as the presence of H-ZSM-5 (Fig. 2a). It is worth noting that the

chlorobenzene conversion outperformed the selectivity of CO2 at the same reaction temperature

during chlorobenzene oxidation (Fig. 2a, b), indicating the generation of abundant by-products

22
(Fig. 2c). In addition, Weng et al. [116] prepared La3Mn2O7 catalyst with and without

phosphoric acid treated for the oxidation of dichloromethane. The catalytic activity of

La3Mn2O7-P outperformed that of untreated one, due to the abundance of proton donors and

Mn (IV) species. The T50% over La3Mn2O7 and treated La3Mn2O7 were 390°C and 355°C

(12,000 mL g−1 h−1), respectively. Also, the corresponding reaction rate over treated La3Mn2O7

was much higher (0.068 μmol g-1 s-1), compared to that of La3Mn2O7. Beside, Yang et al. [117]

prepared Cu doped octahedral manganese oxide molecular sieve (OMS) as catalysts for the

of
catalytic degradation of hexachlorobenzene, compared with the undoped one. Cu(0.4)-OMS

ro
demonstrated enhanced catalytic activity, in which the TOFMn was 6.3×10-3 s-1, however, the

TOFMn of undoped OMS was as low as 0.9×10-3 s-1. The improved catalytic performance of Cu-
-p
OMS could be assigned to the formation of Cu-O-Mn structures, in which the lattice oxygen was
re
activated as well as the surface chloride was rapidly catalyzed by CuO species.
lP

Although noble metal supported catalysts have the advantages of excellent catalytic activity,

it still suffers from serious problems, such the easy deactivation, the generation of Cl-byproducts
na

and the emission of more toxic polychlorinated pollutants, hence restraining the extensive

application of those catalysts toward the elimination of CVOCs. Among noble metal catalysts,
ur

supported Pt, Pd and Ru catalysts are widely studied for the catalytic oxidation of CVOCs. Taking
Jo

chlorobenzene oxidation as an example, Brink et al. [118] synthesized Pt/Al2O3 catalyst for

chlorobenzene destruction, and found that large amount of polychlorinated benzene byproducts

was generated. The main reason is that Pt/Al2O3 would react with dissociated chlorine to form

PtOCl species, and then secondary chlorination occurred between chlorobenzene adsorbed on the

catalyst surface and PtOCl species, thus deactivating catalysts. Besides, Lamonier et al. [119]
23
reported that a series of Pd/ZrO2-TiO2 catalysts were prepared for chlorobenzene oxidation, and

found that the stronger the acidity of the support, the lower the selectivity of polychlorinated by-

products. On the whole, noble metal supported catalysts are not suitable for the oxidation of

halogenated VOCs owing to the easy deactivation poisoned by the chlorine/chloride products.

2.5. N, S-containing VOC elimination

Nitrogen-containing VOCs (NVOCs) (amine-, amide-, nitro- and nitrile- compounds) or

sulfur-containing VOCs (SVOCs) (methyl mercaptan (CH3SH), dimethyl disulfide (DMDS,

of
(CH3)2S2) and dimethyl sulfide ((CH3)2S)) are generated from human behaviors as well as fossil

ro
fuels [1],[120]. It should be pointed out that N- or S- VOCs are also universally employed as raw

-p
materials in industrial production processes. These two sorts of VOCs have seriously nuisance

odors and are responsible for environmental hazards and human health damages. NVOCs are
re
usually inhaled by the body in the form of gas or entered into the body through skin contact, which
lP

pose a serious threat to the human health [120]. The key objectives for catalytic destruction of

NVOCs are high selectivity to N2 and the control of NOx generation to avoid secondary pollutions.
na

Among the catalysts, the active phase of Ce, Cr, Cu, Mn, Sb, Co, Fe, V and Ni are usually loaded

on the supports of zeolite, γ-Al2O3, SiO2, TiO2 and pillared interlayered clay (PILC) to form non-
ur

noble metal catalysts; but Pd, Ag and Pt can be also supported on zeolite to fabricate the noble
Jo

metal supported catalysts [3].

For example, Zhang et al. [120] prepared a series of SBA-15-based catalysts, and the

acetonitrile (CH3CN) conversions over these catalysts followed the order of Pt/ > Pd/ > Cu/ > Co/

> Fe/ > V/ > Ag/ > Mn/ > SBA-15. Although Pt/ and Pd/ SBA-15 catalysts possessed better

catalytic activity, the selectivity of N2 over Cu/SBA-15 is superior to that of Pt/SBA-15 or

24
Pd/SBA-15. As a comprehensive consideration, Cu/SBA-15 is regarded as an excellent candidate

for the elimination of CH3CN, in which an almost complete conversion associated with a N2

selectivity around 80% was achieved at 350°C (20,000 h-1). It is concluded that although noble

metal supported catalysts have superior catalytic activity for NVOC oxidation, especially for nitrile

compounds oxidation, the control of NOx generation is much poorer than that of non-noble metals

[120-122].

It is observed that the physicochemical properties and acid sites of the catalyst have a

of
critical influence on catalytic activity toward NVOC oxidation. For instance, Huang et al. [123]

ro
prepared a series of catalysts for the removal of N-butylamine, ethylenediamine and acetonitrile.

It was found that CrCe/Al2O3/Ti-PILC and CrCe/Ti-PILC had superior catalytic activity for N-
-p
butylamine oxidation, in which T90% were as low as 223°C and 234°C (20,000 h-1). Also, the
re
reaction rates were calculated to be 0.141 and 0.113 μmol g-1 s-1, respectively (reaction

temperature of 180°C). The excellent catalytic performance could be ascribed to larger surface
lP

area, proper acid sites and more mesoporous structure of the catalysts. Besides, N-butylamine was
na

easier to be oxidized over CrCe/Ti-PILC catalyst owing to the proper adsorption strength of

reactant on the acid sites of this catalyst, in comparison with ethylenediamine and acetonitrile
ur

oxidation. All the catalysts demonstrated a good control of NOx generation, limiting the NOx yield

within 2%.
Jo

SVOCs have notorious and irritant odors, and will irritate skin and eyes even at very low

concentrations. The catalytic destruction of SVOCs will generate sulfur byproducts, and form

metal sulfates, leading to poisoning and subsequent deactivation of the used catalysts [124].

Therefore, the rational design and fabrication of catalysts with the characteristics of high catalytic

25
activity, good resistance to sulfur poisoning and superior selectivity to SO2 are of significant

importance [125]. Generally, noble metal supported catalysts have poor resistance to sulfur

poisoning during the catalytic degradation processes, in comparison with the non-noble metal

catalysts. It is generally accepted that the acidity of catalytic materials has a crucial effect on the

catalytic stability for the oxidation of SVOCs. For example, Darif et al. [126] reported that PtCu/Al

had better catalytic activity than PtCu/AlSi20, in which T90% of 310°C (76,500 h-1) and reaction

rate of 0.429 μmol g-1 s-1 over 0.3PtCu/Al were obtained. However, the PtCu/AlSi20 exhibited

of
predominant stability after 30 h of on-stream reaction, which was far better than 6 h of on-stream

ro
reaction of PtCu/Al catalyst. The reason could be ascribed to the enhanced surface acidity of AlSi20

support. It is worth noting that the selectivity of SO2 was 100% over both catalysts, indicating that
-p
no other sulfur byproduct is generated. In addition, Cammarano et al. [127] claimed that HZSM-
re
5 as a catalyst was employed for the oxidation of methyl mercaptan (CH3SH), but the catalyst

would be deactivated after only 10 h. The reason was ascribed to strong acid sites beneficial to the
lP

generation of coke deposits on the surface of HZSM-5. Hence, doped HZSM-5 with the doping of
na

some rare earth metals (La and Sm) were designed for the elimination of CH3SH, in which the

catalytic stability of the catalysts were obviously enhanced and could operate steadily for 80 h of
ur

onstream reaction [128,129]. The characterization results manifested that the amount of acid

site in the catalysts decreased a lot after the doping of La and Sm.
Jo

It is reported that the introduction of hydration water on a catalytic material has a key

influence on the catalytic activity toward the oxidation of SVOCs. Cellier et al. [124] showed

that MnSO4·H2O is more active and sulfur resistant than γ-MnO2 for the catalytic oxidation of

CH3SH owing to the presence of hydration water. The conversion of CH3SH over MnSO4·H2O

26
and γ-MnO2 were 100% and 22% at the temperature of 100°C (60,000 mL g−1 h−1), and the

corresponding reaction rate were calculated to be 0.152 and 0.037 μmol g-1 s-1, respectively,

exhibiting higher degradation efficiency of MnSO4·H2O. The accumulation of sulfate species on

the surface of γ-MnO2 were responsible for the decrease of catalytic activity of the catalyst.

Furthermore, Tanabe et al. [130] also reported that the acidity and acid-base activity of various

transition-metal sulfates including manganese sulfate highly depended on their content of

hydration water. Collectively, for the transition metal oxide catalysts, the acidity and hydration

of
water of the catalysts both have a crucial impact on the SVOC catalytic elimination.

ro
3. Mechanisms based on experimental and theoretical studies
-p
For the gas-solid heterogeneous catalytic reactions, the degradation processes can be divided

into three steps [11,52]. Firstly, the reactants are adsorbed and activated on the surface of catalysts.
re
Secondly, some intermediates are produced through the oxidation of the reactants on the catalysts.
lP

Lastly, the final products are generated and desorbed from the catalysts, and thus the catalysts can

be recovered. Therefore, catalytic elimination processes and/or pathways of VOCs over

na

heterogeneous catalysts should be demonstrated on the basis of oxidation mechanisms, which are

obtained from the studies of experiments and theories. Unexpectedly, although numerous studies
ur

have been investigated in probing the catalytic elimination of different sorts and sources of VOCs,
Jo

comprehensive VOC oxidation mechanisms referring to the degradation processes have been

rarely summarized detailedly. Accordingly, catalytic oxidation kinetics, in situ online analysis and

theoretical simulation calculations are systematically outlined to help researchers understand the

oxidation mechanisms of VOCs in this review.

27
3.1. Catalytic oxidation kinetics

Recently, kinetics of VOC catalytic oxidation on the basis of degradation processes are

widely studied. Generally, three kinetic mechanisms are proposed to evaluate catalytic reaction

steps of VOCs [1,3,131]: Eley-Rideal (E-R) mechanism (Fig. 3a), in which the catalytic process

occurred between adsorbed oxygen species and VOC molecules in gas-phase (or between

adsorbed VOC molecules and oxygen in the gas-phase); Langmuir-Hinshelwood (L-H)

mechanism (Fig. 3b), in which the reaction occurred between adsorbed oxygen species and

of
adsorbed VOC molecules. Based on the same or different active sites of oxygen species and VOC

ro
molecules adsorbed on, the L-H mechanism can be divided into single-site and dual-site ones;

Mars-van Krevelen (MVK) mechanism (redox mechanism) (Fig. 3c), in which the reaction
-p
process occurred between adsorbed VOC molecules and surface lattice oxygen on the catalysts,
re
resulting in the formation of oxygen vacancies. The reduced sites were subsequently re-oxidized

by oxygen in gas-phase or oxygen from the bulk. The oxidative-reductive rates should be the same
lP

in a balanced state for the catalytic oxidation.

na

The validity of each oxidative kinetic mechanisms for VOC oxidation lies on the nature of

VOCs and the property of catalysts. For example, E-R mechanism is suitable for these kinds of
ur

catalytic reaction materials, in which the catalyst supports are usually inert or less reactive toward
Jo

VOC oxidation, such as zeolite, eggshell, activated carbon, Al2O3, silica, etc. [132,133]. The

active sites being supported are usually noble metals or transition metals. For instance, Zabihi et

al. [134] employed E-R mechanism to elucidate oxidation kinetics of cyclohexane over AC-

supported Co catalysts. In addition, the catalytic oxidation process of trichloroethylene (TCE) over

Pd/alumina could be also explained by using E-R mechanism [135]. It is worth noting that catalytic
28
oxidation of different VOCs over the same catalyst follows different catalytic kinetic mechanisms

in some cases. For example, the oxidation of o-xylene over Pt/γ-Al2O3 catalyst could be explained

via L-H mechanism, however, the kinetics of cyclooctane oxidation over the same Pt/γ-Al2O3 was

interpreted by E-R mechanism [132].

The L-H mechanism is also widely used for the explanation of some types of VOC oxidation

over catalytic materials, in which the used catalysts are similar to that of E-R mechanism. For

example, the oxidation of toluene over activated carbon-based Pd catalyst could be elucidated

of
using L-H mechanism [37]. Thybaut et al. [136] reported that the propane oxidation over CuO-

ro
CeO2/γ-Al2O3 catalysts was also well explained via the L-H mechanism. Todorova et al. [137]

demonstrated that the kinetic behaviors of n-hexane elimination over single-site Mn and bi-site
-p
Co-Mn supported on silica catalysts followed an MVK mechanism, nevertheless, the oxidation of
re
n-hexane over single-site Co supported on silica was proceeded via L-H mechanism. Similar

results were also reported by Kaichev and co-workers, in which the kinetic study of propane
lP

oxidation over metallic Ni could be interpreted via L-H mechanism [138]. However, the proceed
na

over NiO was suitable for MVK mechanism, since the lattice oxygen of NiO were participate

in the redox reaction with the adsorbed propane molecules.

ur

It has been generally accepted that the kinetics of VOC oxidation over different metal

oxides or metal-oxide-based catalysts are normally followed the MVK mechanism, in which
Jo

lattice oxygen species plays a critical role in the oxidation of VOCs [139]. Taking CeO2 as an

example, Guo et al. [22] demonstrated that the oxidation of benzene over Pd/kit-CeO2 catalysts

could be explained by the MVK mechanism due to the reduction-oxidation (redox) process

between Ce3+ and Ce4+ of the CeO2-based catalyst. In addition, the Ce-O bond could be greatly

29
weakened through the loading of bio-Pd on the kit-CeO2 surface, and thus enhanced the catalytic

activity of the catalyst. Besides, Genuino et al. [73] reported that manganese oxides were used for

the oxidation of ethylbenzene, benzene, toluene and xylenes, and CuO/Mn2O3 mixed oxides could

be well explained by the MVK mechanism. Similar results were also expressed for benzene

destruction over the NiMnO3/CeO2/Cordierite catalyst [140]. It is surprising that the MVK

mechanism can be also applied in some kinds of supported catalysts, in which the supports are

inert, such as Al2O3, ZSM-5, saponite, zeolite. For example, the MVK mechanism was observed

of
to be well fitted for the catalytic kinetic data of benzene, toluene and o-xylene oxidation over

ro
Ce-Cu/γ-Al2O3 catalysts [141]. In addition, Jabłońska et al. [96] reported that the reaction

kinetics of HCHO, CH3OH and CH4 oxidation over Pd supported zeolite catalysts were well
-p
explained via MVK mechanism because of the reduction-oxidation (redox) process between
re
Pd0 and Pd2+ of the Pd active sites. Similar result was also demonstrated by Hao and co-workers

for the oxidation of benzene, toluene, ethyl acetate over Pd/ZSM-5 catalysts [142]. In addition,
lP

by combining MVK mechanism with H2-TPR, the interaction between Pd NPs and kit-CeO2 of
na

Pd/kit-CeO2 catalyst could be well demonstrated [22].

3.2. In situ online analysis

ur

The in situ online analysis is another analytical method to unveil the reaction mechanisms
Jo

during VOC degradation process. In situ online characterizations, such as in situ FTIR/DRIFTS,

GC-MS, PTR-TOF-MS etc., can be employed as useful techniques to detect active oxygen species,

migration and transformation of the intermediate species as well as final products for VOC

oxidation over the catalytic materials. Therefore, the reaction mechanism for VOC elimination can

be acquired and summarized. For example, Jiang et al. [143] reported that CoOx-CeO2 catalyst

30
was employed for the plasma-catalytic oxidation of toluene. The possible intermediates during the

elimination process were monitored by using GC-MS, and then the surface reaction mechanism

of toluene degradation was speculated. In addition, reaction mechanism for toluene abatement

based on GC-MS measurements was also assessed, and the relevant data was presented in Fig.

4a, indicating the generation of numerous intermediates [144]. It is worth noticed that with the

increase of reaction temperature, the intensity of intermediates decreased, due to the fast

transformation of these species under high temperature. Therefore, the reaction mechanism was

of
proposed as following (Fig. 4b): Firstly, active oxygen species were generated through the

ro
oxygen vacancies and migrated to the catalyst surface; Secondly, the catalytic reaction

happened between toluene and active oxygen species to produce intermediates, which were
-p
oxidized into CO2 and H2O at high temperature; Thirdly, the catalysts were re-oxidized by
re
adsorption and activation of gaseous O2, resulting in the generation of active oxygen species

once again.
lP

Although GC-MS technique is widely employed for the measurement of VOC oxidation
na

process in recent years, it has certain disadvantages, such as the need of labor-intensive sample

preparation and long-time of a single analysis [145,146]. More importantly, this technique cannot
ur

perform a quantitative analysis of some intermediates without standard substances, which largely
Jo

limits its realistic application [147]. Recently, some new MS techniques are introduced and

applied, such as selected-ion flow-tube mass spectrometry (SIFT-MS) and proton transfer reaction

mass spectrometry (PTR-MS). Especially, PTR-TOF-MS techniques in coupling time-of-flight

(TOF) with PTR-MS can be regarded as an excellent alternative, in which it can record the whole

mass spectra of complex VOC species with high mass resolution in real time [148]. For example,
31
Cappellin et al. [148] demonstrated that PTR-TOF-MS technique could be used to estimate

reaction rate coefficients between H3O+ and VOCs at the PTR-MS working conditions. The results

were in agreement with the corresponding theoretical predictions, indicating the accurate

measurement of PTR-TOF-MS method.

As for in situ FTIR/DRIFTS techniques, taking benzene oxidation as an example, Guo et

al. [11] reported that the reaction mechanism of benzene oxidation over Ag/eggshell could be well

interpreted using in situ FTIR technique. The result demonstrated that the active oxygen species

of
of the catalyst were responsible for the benzene oxidation, and oxygen in gas-phase could be

ro
continuously transformed into active oxygen species through role of the catalyst. The produced

intermediates were detected during the catalytic benzene oxidation process, such as phenolate,
-p
benzoquinones, maleate, acetate, etc. Hence, the reaction mechanism were demonstrated by
re
combining in situ FTIR and other characterizations (Fig. 5a): (A) Benzene first reacted with the

active oxygen species and oxidized into phenolate species; (B) The benzoquinones species were
lP

further generated; (C) The carboxylate species could be formed through the cleavage of benzene
na

rings of benzoquinones species; (D) CO2 and H2O were generated by the further oxidation of

carboxylate species.
ur

In addition, Sun et al. [149] reported that the complete catalytic oxidation of HCHO over

Rh/TiO2 catalysts could be achieved at ambient temperature, and in situ DRIFTS was used to
Jo

speculate catalytic oxidation mechanism of HCHO. Different in situ DRIFTS experiments were

operated to demonstrate the adsorption of HCHO and subsequent catalytic reaction between

HCHO and O2 or O2 + H2O on Rh-based catalysts. The intermediates, final products, oxygen

species as well as OH species were detected and analyzed. Therefore, the catalytic oxidation

32
pathway of HCHO could be deduced (Fig. 5b), and H2O and OH species played an important role

for HCHO oxidation over TiO2-supported Rh catalysts. Similar result could be also obtained by

Deng et al. [35], in which in situ DRIFTS, CO-TPD and C6H6-TPD were employed for the

explanation of surface oxidation mechanism of benzene. It was found that the generation and

consumption rate of carbonate species (ad CO32-) of Pd-Ceramic-S were higher than that of Pd-

Glass-S under the same conditions, and Pd-Ceramic-S catalyst was more active than Pd-Glass-S.

Collectively, the above examples demonstrated that the in situ FTIR/DRIFTS characterization is

of
an effective candidate to clarify the oxidation mechanism of VOCs on different catalytic materials.

ro
For practical industrial emissions, on one hand, more than one VOC can be detected; on the
-p
other hand, industrial VOCs usually contain a large amount of impurity gases, such as H2O, CO2,

SO2. For instance, as many as 32 kinds of VOCs were detected in the atmosphere near
re
pharmaceutical companies in Shijiazhuang, Hebei Province, China [150]. Hence, considering the
lP

characteristics of practical industrial emission, the studies on catalytic oxidation mechanism of

VOC mixture or in the presence of impurity gases are needed. However, the majority of literatures
na

on catalytic oxidation mechanisms are single VOC, few studies are related to VOC mixture or

VOCs along with impurity gases. Recently, Wang et al. [50] prepared a series of Pt/TiO2 catalysts
ur

for catalytic combustion of toluene, acetone and their mixture. By employing TD-GC/MS and in
Jo

situ DRIFTS techniques, it is demonstrated that the catalytic mechanism of the oxidation of toluene

and acetone mixture is the same with those of toluene or acetone. Thus, the reaction pathway for

the abatement of VOC mixture might also follow the catalytic oxidation process of single toluene

and acetone (Fig. 6). In addition, the catalytic mechanism of VOC oxidation in the presence of

H2O, CO2 and SO2 were also studied by the same group [151]. Although the introduction of
33
H2O, CO2 and SO2 slightly inhibited the catalytic activity and stability of Pt/TiO2 for toluene

oxidation, these molecules does not alter toluene oxidation pathway via the operation and

analysis of GC-MS as well as in situ DRIFTS. It is concluded that the co-presence of multiple

VOCs or the introduction of impurity gases do not change the catalytic mechanism and reaction

pathway toward VOC elimination.

3.3. Theoretical simulation calculations

of
Among these theoretical simulation techniques employed for VOC elimination, DFT

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calculations are the most popular technique to demonstrate the catalytic mechanism by

fabricating theoretical models, And thus the adsorption site and adsorption energy, activation
-p
barrier, geometric and band structure, electronic densities as well as density of state can be
re
demonstrated [149,152]. In order to confirm the adsorption sites of VOC molecules on the noble

metal supported catalyst as well as the effect of pore structure of the support on catalyst
lP

performance, DFT simulation calculations of three models including non-porous, small porous

and large porous Pd55/CeO2 models were built for the adsorption and activation of benzene
na

molecules [22]. The calculation results found that benzene molecules were all preferred to

adsorb on Pd55 other than CeO2 support or interface sites (Fig. 7), indicating that the Pd55 are
ur

the adsorption sites of VOC molecules over Pd55/CeO2 catalysts. In addition, the adsorption
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energy of non-porous, small porous and large porous Pd55/CeO2 were calculated, which were

1.71, 1.84 and 1.54 eV, respectively. The bigger the value of adsorption energy, the stronger

the activation ability of catalysts. Therefore, the pore structures of the support play an important

role in preparing noble metal supported catalysts for VOC oxidation.

34
 Besides, Mao et al. [153] also reported that the DFT calculations could effectively elucidate

the influence of Pt NPs size on the catalytic activity of the catalyst. As shown in Fig. 8a,b,

Pt9/Ce33O66 and Pt6/Ce33O66 are designed by placing a large cluster of Pt9 and a small cluster of Pt6

into the nanopore of Ce33O66 slabs, respectively. The results found that EOV for Pt9/Ce33O66 and

Pt6/Ce33O66 is 1.68 and 1.40 eV, respectively. It is widely accepted that the smaller the EOV value,

the stronger the catalytic activity of catalysts. The result indicated that small Pt NPs size of the

catalyst was more beneficial for the catalytic oxidation of VOCs. In addition, Wang et al. [51]

of
established theoretical slab models for the (001) and (110) surfaces of 3D-hm LSMO catalyst

ro
toward methane oxidation. The calculated results of cleavage energy, adsorption energy and

energy barrier all demonstrated that the exposed (001) surfaces of the catalyst were conductive
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to methane degradation, compared to that of the exposed (110) surfaces. These obtained results
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were consistent with the experimental data of catalytic methane oxidation over different

catalyst.
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4. Reactors for VOC elimination

The catalytic reactors can be regarded as support of the catalyst used for VOC oxidation,
ur

and the design and fabrication of a cost-effective reactor is also critical in the realistic industrial

process [40]. Among the three catalytic reactors of continuous-flow fixed-bed, membrane and
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fluidized-bed, the continuous-flow fixed-bed reactors are most commonly used for VOC

catalytic destruction. The catalysts employed in this reactor can be usually divided into particle-

shaped catalysts and monolithic/foam-shaped catalysts, respectively [3]. The particle-shaped

catalysts with continuous-flow fixed-bed reactors are suitable for lab-scale evaluations toward

35
VOC elimination, in which it has the advantages of low catalyst usage, low energy consumption

and simple operation conditions. For example, Liu et al. [27] employed continuous flow fixed-

bed microreactor for the catalytic oxidation of VOCs over Au/Co3O4 catalysts with the particle

diameter of 40-60 mesh. The T90% for benzene, toluene, o-xylene were 189°C, 138°C and 162°C,

respectively. Similar results were also observed from these kinds of reported literatures [154-156].

However, particle-shaped catalysts have the disadvantages of high diffusion resistance, low

gas-solid contact and more importantly low amount elimination efficiency of VOCs, and thus

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were not suitable for large-scale application in industrial processes.

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Recently, the structured catalysts, such as monolithic and foam-shaped catalysts, are

considered to be an alternative, which can obviously enhance catalyst-VOCs contacting

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efficiency, improve the attrition resistance and reduce reactor pressure [157]. The monolithic
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and foam-shaped catalysts with continuous-flow fixed-bed reactors are usually designed and

applied for small-scale industrial emission sources of high concentration VOCs with the
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characteristics of high-efficiency, safety and decentralization. For example, Ribeiro et al. [40]
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reported a pilot-scale catalytic reactor for the destruction of toluene over a honeycomb shape

commercial catalyst (Pd-Ba/Al2O3) (Fig. 9). Several catalytic parameters of toluene oxidation
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were explored. The results showed that reaction temperature was proved to be the most

important process variable for toluene oxidation efficiency, and the higher the reaction
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temperature, the shorter the space time. Similar report is also reported by Duplančić et al. [158],

in which the monolithic manganese-nickel mixed oxide catalysts had superior catalytic activity

for toluene oxidation, compared to powder-formed catalysts. In addition, ceramic, metallic

36
alloy foam and pillared clays wash-coated with active phases as monolithic catalysts were also

observed and reported for various VOC abatement [159-161].

Although continuous-flow fixed-bed reactors based on monolithic catalysts are widely

employed in industrial process, it still suffers low elimination efficiency of VOCs due to the

relatively poor contacting efficiency between VOCs and catalysts [42,157]. Membrane reactor,

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another kind of fixed-bed reactor, can significantly enhance the contacting efficiency by

introducing membrane materials onto the catalysts. For this kind of reactor, alumina tubular

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supported ZSM-5 membranes [162], the zeolite coated cordierite foams [163] and aluminum
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foam [164] are normally adopted as structured supports for dispersing active phase on catalysts.

The membrane reactor has the advantages of excellent reaction stability, good contacting
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efficiency, reasonable mass/heat transfer efficiency, low diffusion resistance as well as small bed
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pressure drop. For example, a structured zeolite membrane reactor based on a Cu-Mn/ZSM-

5/PSSF catalyst [41,165], was designed and fabricated to enhance the catalytic degradation of
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isopropanol (Fig. 10), giving a T90% of 70°C much lower than that of the traditional fixed-bed

reactor. Similar result could be also observed by Benard et al. [166], in which the membrane
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reactor performed better than the tubular fixed-bed reactor for the destruction of propane and
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toluene over Pt/Al2O3. Hence, membrane reactor may be also a promising candidate for the

removal of industrial VOC emissions in the future.

As another type of reactor, fluidized-bed reactors are also employed for the catalytic

oxidation of VOCs, which have the advantages of uniform temperature distribution, well dispersed

37
active phases and good VOCs-catalysts contact efficiency [167]. Nowadays, the majority of the

published literatures involving this kind of reactors are related to photocatalytic degradation of

VOCs over catalytic materials [168]. As for VOC (thermo)catalytic oxidation, Syed-Hassan et al.

[167] reported catalytic destruction of ethane over fluidized NiO nanoparticles catalyst, and found

that catalyst without the use of support could significantly reduce the catalytic volume of the

reactor used, thus resulting in savings in the fabrication and operating costs. The NiO nanoparticles

demonstrated some different characteristics for the desorption of ethyl radicals during ethane

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oxidation process, compared to porous NiO/SiO2.

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5. Photothermocatalytic oxidation of VOCs
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Generally speaking, catalytic oxidation technology can be mainly divided into

thermocatalysis and photocatalysis. Although thermocatalytic oxidation of VOCs has the

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advantages of high activity, good selectivity as well as excellent durability of the employed
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catalytic materials, high energy consumption is still required for the efficient destruction of

refractory VOCs due to the high reaction temperature needed. In contrast, photocatalytic
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technology can use inexhaustable solar energy for air pollutant purification under mild

conditions [169-172]. However, among photocatalytic technology, photocatalytic oxidation

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usually suffers from seriously low degradation efficiency of VOCs [173-175]. Thus, considering
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the high energy consumption of thermocatalysis and the low degradation efficiency of

photocatalysis, the combination of thermalcatalysis with photocatalysis has been regarded as an

emerging candidate. Recently, much lower temperature with equal or even higher activity can be

obtained on the photothermocatalysts owing to the synergetic oxidation effect [48,176]. At

38
present, most of the VOC photothermocatalytic oxidation are conducted in a batch mode, in

which air pollutants in a rector can be completely oxidized at certain time [177].

For the evaluation metrics of VOC photothermocatalytic degradation, the concepts of

quantum yield (QY), quantum efficiency (QE) and space-time yield cannot be used firsthand, since

the two metrics are designed for the systems operating only on pure photocatalytic systems [9].

Given on the characteristics of hybrid processes by combining both photocatalytic and

thermocatalytic approaches, a figure of merit (FoM) is proposed to evaluate the catalyst

of
performance under batch-mode systems, in which the unites are normalized and all the variables

ro
are considered [9]. The equation of FoM is presented as follows:
XVOCs
FoM = (2)
m × CVOCs × t ×P -p
Where XVOCs (%) is the conversion efficiency of VOCs, m (mg) is the mass amount of the
re
catalyst, CVOCs (ppm) is initial concentration of VOCs, t (min) is the irradiation time, and P (W)

is the applied power. Generally, the FoM values are based on five operational parameters that
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are taken into account all the variables under photothermocatalytic conditions, and thus the
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actual performance of catalysts can be accurately evaluated. Currently, FoM has been often

employed to evaluate the catalyst performance of aqueous photocatalytic systems [178-180].

ur

Nevertheless, this equation is rarely applied for VOC photothermocatalytic degradation [9].

Generally speaking, the photothermocatalysts can be divided into two types: one is the noble
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metal supported catalysts with the properties of excellent thermalcatalytic activity of noble metals

and the photo-induced features of the semiconductor metal oxides; another is metal oxide catalysts

which have both the properties of thermalcatalytic activity and photo-induced features [176,181].

The relevant parameters and the corresponding FoM values of photothermocatalytic elimination

39
of various VOCs are conducted for the performance comparison of different catalysts (Table 2).

Among various catalysts, noble metal supported catalysts are extremely interesting for the efficient

photothermocatalytic elimination of VOCs due to their excellent catalytic activity and strong

regeneration ability. Loading noble metals onto a semiconductor support can generate a schottky

barrier to hinder charge recombination and capture the photogenerated electrons, thus leading to

the enhanced photothermocatalytic activity over noble metal supported catalysts [182-184]. The

performance of such catalysts is highly related to the synergetic effect between thermocatalysis

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and photocatalysis. For example, Li et al. [174] reported that Pt/TiO2 demonstrated excellent

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photothermal performance for benzene degradation, in which the FoM was calculated to be

3.31E-07. Surprisingly, the photothermocatalytic durability of this catalyst outperformed that

-p
under photocatalytic or thermocatalytic conditions alone. In addition, Pt-loaded TiO2/ZrO2
re
exhibited inferior photothermocatalytic performance for the oxidation of benzene (FoM of

5.55E-09) [185], The poor performance of the catalyst could be attributed to the mode of used
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catalysts in the reactors. Also, similar results relating to photothermocatalytic degradation of

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VOCs were demonstrated by other studies [48,186]. It is concluded that the highest FoM value

(3.31E-07) was achieved for benzene photothermocatalytic degradation over Pt/TiO2, exhibiting
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good photothermocatalytic performance of this catalyst (Table 2).

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Metal oxide-based catalysts are also widely employed for VOC degradation under

photothermocatalytic conditions owing to their low cost and relatively high degradation

efficiency. Among these catalysts, fabricating photothermocatalytic nanocomposites by

combining metal oxides with photocatalyzedly activated TiO2 is an effective method. For

40
example, Ma et al. [181] synthesized MnOx/TiO2 nanocomposites for photothermocatalytic

degradation of benzene under the irradiation of a Xe lamp. The catalyst showed good activity

and stability for benzene oxidation, in which the regeneration capabilities were up to 25 cycles

and FoM value was 4.46E-08. The reason could be ascribed to synergetic effect between the

thermocatalysis on CeO2 and the photocatalysis on TiO2. In addition, Yang et al. [190]

investigated benzene photothermocatalytic oxidation over R-MnO2-HS. As shown in Fig. 11a, the

CO2 production rate of this catalyst with the solar light irradiation were significantly improved, in

of
comparison with that in the dark, ascribed to the synergetic effect between solar light driven

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thermocatalysis and photoactivation. The FoM value was calculated to be 1.54E-08. In addition,

the solar light driven thermocatalysis mechanism was systematically demonstrated (Fig. 11b).
-p
Perovskites are another kind of metal oxide-based catalyst, which have been also applied for
re
VOC degradation in recent years. Apart from the application of thermocatalytic destruction of

VOCs, the photothermocatalytic oxidation of VOCs has also attracted numerous attentions. For
lP

example, Chen et al. [21] synthesized a series of ABO3-type perovskites by using the soft-
na

templating method for styrene photothermocatalytic degradation. The results demonstrated that

LaMnO3 had excellent activity and FoM value was as high as 1.55E-07, ascribed to the synergetic
ur

effect between photocatalysis and thermocatalysis. Besides, the rate constant of styrene

degradation was 0.0782 min-1, also higher than 0.0054 min-1 for phototcatalytic degradation or
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0.0263 min-1 for thermocatalytic oxidation. Likewise, CeMnxOy/TiO2 also exhibited superior

photothermocatalytic activity and stability for benzene elimination, in which the regeneration

capabilities could be 25 cycles and FoM value was calculated to be 9.25E-08 [24]. Among metal

oxide-based catalysts, LaMnO3 demonstrated excellent photothermocatalytic performance for

41
styrene oxidation, which can be regarded as an alternative for VOC degradation in realistic

applications.

For the purpose of real industrial applications, the continuous-mode photothermocatalytic

systems of VOC elimination are become more and more popular in recent years, since large

amounts of VOCs can be eliminated over catalysts uninterruptedly. For instance, Kong et al.

[176] reported that PtCu/CeO2 demonstrated outstanding activity for n-pentane degradation

of
under photothermocatalytic conditions, in which the complete mineralization of n-pentane

could be achieved at about 400°C under photothermocatalysis, 200°C lower than that of single

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thermocatalytic elimination. Also, the activation energy of n-pentane oxidation was reduced to
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20.1 kJ mol-1 under simulated solar irradiation. The excellent activity of PtCu/CeO2 could be

ascribed to the intensification of thermocatalysis oxidation by photocatalysis as well as the

re
enhanced photocatalysis by thermocatalysis efficiency. As for metal oxide-based catalyst, CeO2
lP

catalyst was prepared and demonstrated superior photothermocatalytic activity and durability

toward styrene oxidation [191]. The activation energy of styrene oxidation was as low as 15.6 kJ
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mol-1 for CeO2 under photothermocatalytic system, which was obviously lower than that under

thermocatalytic system (48.2 kJ mol-1). From the above discussion, it is concluded that the VOC
ur

photothermocatalytic activity of nanoparticles catalysts outperforms that under photocatalytic or

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thermocatalytic conditions alone. However, compared with pure thermocatalysis, the

improvement effect of photothermocatalysis for VOC elimination is not very obvious. Therefore,

the reaction mechanism of VOC photothermocatalytic elimination over catalysts are worth

studying in future.

42
 Currently, the synergetic mechanisms for the VOC photothermocatalytic oxidation are

mainly explained based on the surface plasmon effect and the MVK mechanism. Surface

plasmon effect is usually applied in noble metal-based or semiconductor oxides catalysts. Zou

et al. [192] concluded that the enhanced photothermocatalytic activity of Pd/CeO2 for toluene

oxidation was due to the hot electrons, which were generated through strong surface plasmon

resonance of Pd under irradiation. The hot electrons were rapidly transferred to the CeO2

through the Pd-CeO2 interface, prolonging the life of the hot electrons and thus increasing the

of
temperature of the reaction system. The above behaviors could also enhance the activity of

ro
surface adsorbed oxygen and lattice oxygen and then promoted catalytic activity of the catalyst.

In addition, Mao et al. [193] pointed out that the photothermocatalytic synergetic degradation
-p
of benzene, toluene and acetone could be explained by using the MVK mechanism. Kong et al.
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[176] also reported that the photothermocatalytic mineralization of n-hexane over PtCu/CeO2

followed the MVK mechanism, in which the thermocatalytic activity of PtCu/CeO2 can be
lP

enhanced by photocatalysis through the acceleration of the Mars-van Krevelen redox cycle.
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6. Conclusions and perspectives

This review is aimed to provide a comprehensive overview on the catalytic oxidation of

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VOCs by using different nanoparticles catalysts, including noble metal supported catalysts and
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metal oxide-based catalysts. The advantages and recent processes of VOC catalytic elimination

over different kinds of catalysts are summarized and compared, in which reaction rate is adopted

and normalized for the performance comparison of the catalysts between different studies. The

rational design of catalysts based on VOC characteristics are a promising direction for industrial

scale application. Among various catalysts, noble metal supported catalysts are extremely
43
interesting owing to their excellent activity and stability. However, the industrial practical

application of such noble metal supported catalysts has been hindered by their high cost, tedious

preparation and easy deactivation due to S-, Cl- poisoning. As an alternative to noble metal

catalysts, non-noble metal catalysts are becoming more and more attractive owing to the relatively

high catalytic activity, low cost and large-scale industrial application. Besides, VOC oxidation

mechanisms are allsidedly discussed and summarized based on studies of catalytic oxidation

kinetics, in situ online analysis and theoretical simulation calculations, which are helpful for the

of
exploration of VOC degradation pathway, intermediate species, catalyst poisoning, theoretical

ro
degradation process, etc. Also, the catalytic reactors used are analyzed for highly efficient

abatement of targeted industrial VOCs. Photothermocatalytic degradation technology by

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integrating (thermo)catalysis with photocatalysis is regarded as a promising candidate for the
re
efficient elimination of VOCs, and FoM is presented for the performance comparison of catalytic

nanomaterials under batch-mode systems. Although plentiful efforts have been made on the
lP

destruction of different sorts of VOCs by using catalytic oxidation method, there still exist many
na

scientific issues and challenges for the efficient elimination of VOCs.

(i) In real atmospheric environment, VOC mixtures are always emerged along with industrial
ur

emissions. However, most discussions in the published literature on VOC catalytic elimination are

single component oxidation and rarely involve simultaneous oxidation of VOC mixtures.
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Therefore, mutual effect on catalytic oxidation of mixed VOCs should be seriously taken into

consideration, and the better understanding of the interaction among simultaneous oxidation of

VOC mixtures may help researchers develop cost-effective catalytic reactors and fabricate

efficient catalysts for industrial applications.

44
 (ii) Among many VOC elimination techniques, catalytic oxidation technique is most widely

employed and demonstrates the highest degradation efficiency. However, some problems need to

be solved, such as high energy consumption. Hence, hybrid treatments technologies by integrating

the advantages of single technology, such as adsorption-catalytic oxidation, photo-thermo catalytic

oxidation and plasma-catalytic oxidation, can be further investigated for the efficient destruction

of VOCs in the future.

(iii) Currently, the complete catalytic oxidation of VOCs into H2O and CO2 is the most

of
adopted method for VOC elimination. Although this method can efficiently oxidize VOCs, it will

ro
also lead to the waste of resources and CO2 emissions at the same time. Therefore, from the

perspectives of resource utilization and economic benefits, selective catalytic oxidation of VOCs
-p
to useful products has been regarded as an emerging alternative for VOC control in recent years.
re
(iv) In situ online characterizations, such as in situ FTIR/DRIFTS, synchrotron radiation,

isotopic tracer techniques, GC-MS and PTR-TOF-MS, are essential for the exploration of
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oxidation mechanisms. However, these characterizations are usually conducted alone in present
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papers. Therefore, a deeper insight into the combination of these characterization techniques

should be emphasized involving better understanding of the elimination pathways, the reason of
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catalyst poisoning, migration and transformation of intermediate species during VOC degradation

process.
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(v) The majority of catalysts in the available literature on VOC catalytic elimination are

presented in the form of nanoparticles, however, the catalysts used in industrial catalytic reactors

should be prepared in the form of monolith or honeycomb. Hence, it is still a big challenge to

45
prepare monolithic or honeycomb catalysts by putting the nanoparticle-shaped catalyst on proper

substrate while maintaining the activity, selectivity and stability of the catalytic nanomaterials.

The future development of catalytic oxidation technology for the efficient degradation of

VOCs with low cost still remain to be challenged in atmospheric environmental field. In this

regard, it is believed that catalytic nanomaterials designed for industrial VOC elimination under

realistic conditions should be seriously taken into scientific consideration in the near future.

of
Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal

ro
relationships that could have appeared to influence the work reported in this paper.

Acknowledgements
-p
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This work was supported by the National Natural Science Foundation of China (41425015,

41731279 and 21707020), the Local Innovative and Research Teams Project of Guangdong
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Pearl River Talents Program (2017BT01Z032), the Innovation Team Project of Guangdong
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Provincial Department of Education (2017KCXTD012), the Guangdong Provincial Key R&D

Program (2019B110206002) and The Leading Scientific, Technical and Innovation Talents of
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Guangdong special support program (2016TX03Z094). This work was specially contributed to

this special issue in the memory of our beloved colleague and friend, Prof. Maria Flytzani
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Stephanopoulos, for her outstanding contribution to the journal of “Applied Catalysis B:

Environmental”.

CRediT authorship contribution statement

46
 Yunlong Guo: Investigation, Formal analysis, Writing - original draft. Meicheng Wen:

Writing - review & editing. Guiying Li: Writing - review & editing. Taicheng An:

Conceptualization, Supervision, Writing - review & editing.

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Fig. 1. (a) Methane conversion as a function of reaction temperature over different samples. (b) methane

conversion versus temperature with the rise (solid) and drop (empty) in temperature over Pd@Co/CeO2 and

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Pd/CeO2 samples. Reproduced with permission from [90]. Copyright 2016 Elsevier.

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Fig. 2. (a) CB conversions over different kinds of catalysts; (b) mineralization rate analyses in CB oxidation
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over Mn0.8Ce0.2O2/H-ZSM-5 and Mn0.8Ce0.2O2 catalysts. (c) carbon distributions in the out-let gases under

different conditions. Reproduced with permission from [115]. Copyright 2016 Elsevier.

66
 of
Fig. 3. Schematic diagram of (a) E-R mechanism. Reproduced with permission from [1]. Copyright 2019

Elsevier. (b) L-H mechanism and (c) MVK mechanism. Reproduced with permission from [131].

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Copyright 2016 Elsevier.

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Fig. 4. (a) The intermediates generated from toluene abatement under microwave heating by using GC-MS.
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(b) Possible degradation process of toluene vapor using microwave heating. Reproduced with permission

from [144]. Copyright 2019 Elsevier.

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 of
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Fig. 5. (a) The reaction mechanism of benzene oxidation over the Ag/eggshell catalyst. Reproduced with
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permission from [11]. Copyright 2019 RSC. (b) Schematic of proposed reaction pathway for complete

oxidation of HCHO in the presence of H2O over Rh/TiO2 at room temperature. Reproduced with
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permission from [149]. Copyright 2018 Elsevier.
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Fig. 6. Reaction pathways for the oxidation of toluene and acetone mixture. Reproduced with permission
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from [50]. Copyright 2020 Elsevier.

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 of
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Fig. 7. Structure of non-porous, small porous and large porous CeO2 (a-c). the corresponding Pd55/CeO2 (d-

f) and benzene adsorption structure of the catalysts (g-i). Reproduced with permission from [22]. Copyright

2019 Elsevier. -p
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Fig. 8. The super cells for DFT calculation of Pt9/Ce33O66 slab (a) and Pt6/Ce33O66 slab (b). Reproduced with

permission from [153]. Copyright 2016 ACS.

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Fig. 9. Schematic of the pilot-scale catalytic reactor used for the toluene catalytic oxidation over Pd-

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Ba/Al2O3 catalyst. Reproduced with permission from [40]. Copyright 2019 Elsevier.

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Fig. 10. Schematic of the structured zeolite membrane reactor based on Cu-Mn/ZSM-5/PSSF catalysts for
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VOC combustion. Reproduced with permission from [165]. Copyright 2013 ACS.
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Fig. 11. (a) Catalytic activity of R-MnO2-HS toward benzene oxidation at different temperatures with full

solar spectrum irradiation or in the dark. (b) the schematic illustration of solar light driven thermocatalysis.
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Reproduced with permission from [190]. Copyright 2017 ACS.

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 Table 1 Summary of operation condition, conversion temperature and reaction rate of typical
catalysts toward catalytic elimination of benzene-based VOCs
Reaction rate
Reactant Space velocity
VOC type Catalyst T90% (°C) (μmol gcat-1 s-1) Reference
composition (mL·g-1·h-1)
at 190°C

Benzene 19.9Ag/eggshell 1000 ppm, 40% O2, N2 20,000 225 0.025 [11]

1.0Ru-5Co/TiO2 500 ppm, 20% O2, Ar 60,000 215 0.041 [53]

0.25Pt1/meso-Fe2O3 1000 ppm, 20% O2, N2 20,000 198 0.125 [19]

6.5Au/meso-Co3O4 1000 ppm, 40% O2, N2 20,000 189 0.206 [27]

0.5Pd/kit-CeO2 1000 ppm, 40% O2, N2 20,000 187 0.211 [22]

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0.18Pt/eggshell 1000 ppm, 40% O2, N2 80,000 178 0.220 [52]

0.8Pd/Ceramic 1500 ppm, 20% O2, N2 90,000 225 0.842 [35]

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1.0Pt/Al2O3 2800 ppm, air 32,000 144 1.016 [54]

CoMn2AlO

CeO2/LaCoO3
100 ppm, 20% O2, N2

500 ppm, air

-p
60,000

96,000
208

410
0.038

--
[55]

[56]
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ZnCo2O4 498 ppm, 20% O2, N2 90,000 236 0.188 [38]

0.27Pt/3DOM CeO2-
Toluene 1000 ppm, 40% O2, N2 20,000 198 0.122 [57]
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Al2O3

0.13Ag/Mn2O3 1000 ppm, 40% O2, N2 40,000 215 0.250 [32]

3.8AuPd/3DOM-Mn2O3 1000 ppm, air 40,000 162 0.327 [58]

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0.95Pd/Fe-ZSM-5 1000 ppm, air 60,000 178 0.667 [59]

1.0Pt/ZSM-5 1000 ppm, air 60,000 149 0.680 [60]

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LaNiO3 500 ppm, 10% O2, N2 19200 250 0.033 [61]

MnO2 1000 ppm, 40% O2, N2 20,000 225 0.034 [62]

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Co2.25Mn0.75O4 1000 ppm, 20% O2, N2 40,000 214 -- [63]

CeO2-MOF 1000 ppm, air 20,000 223 0.036 [64]

o-xylene 1.0Pd/Co3O4 (3DL) 150 ppm, air 60,000 249 0.002 [65]

0.22Pt/Fe2O3 1000 ppm, 20% O2, N2 40,000 225 0.032 [66]

1.94AuPdFe/Mn2O3 1000 ppm, 20% O2, N2 40,000 213 0.141 [67]

3.7Au/meso-Co3O4 1000 ppm, 40% O2, N2 20,000 191 0.184 [27]

72
 meso-CoOx 1000 ppm, 20% O2, N2 40,000 244 0.018 [68]

8.8Co3O4-MnO2 1000 ppm, 20% O2, N2 100,000 273 -- [69]

CeO2 nanorods 250 ppm, air 60,000 239 0.073 [70]

ethylbenzene 2Pt/MCM-41 4340 ppm, air 15,000 248 0.236 [71]

30Pt/CNT 100 ppm, air 75,000 ＜388 -- [72]

OMS-2 N/A 12,000 342 -- [73]

Mn2O3 N/A 12,000 374 -- [73]

CuO/Mn2O3 N/A 12,000 350 -- [73]

γ-MnO2/SmMnO3 1000 ppm, air 60,000 217 0.150 [74]

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CoMn/AC 1.0 vol.%, air 66,000 250 -- [75]

Naphthalene 1.0Pd/Mγ-Al2O3 100 ppm, 10% O2, He 1220 162 -- [76]

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0.5Pd/3.0V/TiO2 100 ppm, air 45,000 241 0.011 [77]

Ce0.95Zr0.05Ox

CeO2
100 ppm, 20% O2, He

100 ppm, air

-p
45,000

60,000
--

210
--

--
[78]

[79]
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CuZnO 100 ppm, air 60,000 250 -- [79]

Ce0.984Cu0.016O2 450 ppm, 20% O2, N2 75,000 220 -- [80]

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--: No related information obtained from the literature.

Table 2 Summary of batch-mode photothermocatalytic elimination of various VOCs over

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different kinds of catalysts

VOC Catalyst Light power Concentration Conversion Irradiation
Catalyst FoM Reference
type mass (mg) (W) (ppm) (%) time (min)
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Benzene Pt/TiO2 500 300 W Hg UV lamp 67 100 30 3.31E-07 [174]

Toluene Pt/MO 100 500 W Xe solar lamp 200 90 30 3.00E-07 [187]

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Toluene Ag/F-STO 200 300 W Xe lamp 800 100 240 8.68E-09 [188]

Xylene Ag/F-STO 200 300 W Xe lamp 800 100 330 6.31E-09 [188]

Benzene Pt/TiO2-ZrO2 2000 Three 10 W UV lamps 313 100 960 5.55E-09 [185]

Styrene LaMnO3 1300 300 W Xe lamp 40 96.6 40 1.55E-07 [189]

Benzene CeMnxOy/TiO2 100 500 W Xe solar lamp 1081 100 20 9.25E-08 [24]

Benzene MnOx/TiO2 100 500 W Xe solar lamp 1081 96.5 40 4.46E-08 [181]
73
Benzene R-MnO2-HS 100 500 W Xe solar lamp 4324 100 30 1.54E-08 [190]

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74