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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2024 , Vol. 36 >Issue 3: 357 - 366

DOI: https://doi.org/10.7536/PC230724

Review

Photocatalytic Production of Hydrogen Peroxide from Covalent Organic Framework Materials

  • Anqi Chen ,
  • Zhiwei Jiang ,
  • Juntao Tang , * ,
  • Guipeng Yu *
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  • College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
* e-mail:

† These authors contributed equally to this work.

Received date: 2023-07-26

  Revised date: 2023-08-28

  Online published: 2023-09-20

Supported by

Hunan province Funds for Distinguished Young Scientists(2022JJ10080)

Hunan Provincial Science and Technology Plan Project, China(2021GK2014)

National Natural Science Foundation of China(52173212)

National Natural Science Foundation of China(52103275)

Hunan Provincial Natural Science Foundation(2021JJ30795)

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Abstract

Hydrogen peroxide (H2O2) is an important green oxidizing agent, but the main anthraquinone process for production thereof suffers high energy consumption and large safety risks. Artificial photosynthesis H2O2 from water and oxygen features safe, environmentally friendly and energy-saving characteristics and has gradually become a research focus. Covalent organic frameworks (COFs) have been widely used in the photocatalytic production of H2O2 for their high specific surface area, good photocatalytic performance and structural tunability. This review summarizes the recent research progress in the field of COFs photocatalytic production of H2O2, discussing the reaction mechanisms for the production of H2O2 through oxygen reduction, water oxidation, and dual-channel processes. It introduces methods to improve the photocatalytic production of H2O2 by regulating the optical bandgap, enhancing charge separation capability, and improving carrier mobility of COFs through structural design and functional group modification. These methods contribute to the design of efficient, stable, and sustainable COFs for photocatalytic production of H2O2.

Contents

1 Introduction

2 Hydrogen peroxide production by ORR pathway

2.1 Direct one-step two-electron oxygen reduction mechanism

2.2 Indirect two-step single-electron oxygen reduction mechanism

3 Hydrogen peroxide production by WOR pathway

4 Dual-channel path production of hydrogen peroxide

5 Conclusion and outlook

Key words： covalent organic framework; hydrogen peroxide; photocatalysis; oxygen reduction; water oxidation

Cite this article

Anqi Chen , Zhiwei Jiang , Juntao Tang , Guipeng Yu . Photocatalytic Production of Hydrogen Peroxide from Covalent Organic Framework Materials[J]. Progress in Chemistry, 2024 , 36(3) : 357 -366 . DOI: 10.7536/PC230724

1 Introduction

As an important oxidant, hydrogen peroxide （H2O2） is an environmentally friendly and widely used chemical raw material and fine chemicals[1][2]. It can be used in pulp bleaching, sewage treatment, food and medicine, metallurgy and other fields[3][4][5]. According to statistics, China's H2O2 production capacity is increasing year by year, and the global production capacity is expected to reach 5.7 million tons in 2027[6].
The production processes of H2O2 mainly include sulfate electrolysis, isopropanol oxidation, etc. Electrolysis method has the advantages of simple process, high product purity and low impurities, but it is not suitable for large-scale production because of its high consumption of precious metals[7]. Isopropanol oxidation does not require other catalysts, but it consumes a large amount of raw materials and is not competitive[8]. The oxygen cathode reduction method has the advantages of low production cost, simple equipment and no pollution, but the concentration of the prepared H2O2 product is low and the method is not practical[9]. The direct hydrogen-oxygen synthesis method has high atom utilization rate and low production cost, but the potential safety hazard of mixing hydrogen and oxygen has not been solved yet[10]. At present, the mature production method in industry is the anthraquinone method, but there are still the following problems in the large-scale production of high-concentration products, such as the production process is cumbersome, easy to consume a lot of energy, more by-products and difficult to deal with[11].
In contrast, photocatalytic technology has the advantages of environmental friendliness, sustainable energy saving and high catalytic performance, which is conducive to the green production of H2O2. However, most of the reported photocatalysts still have some problems, such as narrow light absorption range, low absorption utilization, and easy and rapid recombination of photogenerated electrons and holes. Therefore, the development of new photocatalysts has always been the focus and focus of scientific research.
Covalent Organic Frameworks (Covalent Organic Frameworks, COFs), as a new type of photocatalyst, have the characteristics of regular structure, narrow pore size distribution, high surface area and π-conjugated structure[12]. The structure-tunable performance of COFs enables the targeted design of photocatalysis, and the high specific surface area and porosity enable the introduction and exposure of more catalytic sites. Therefore, more and more COFs have been successfully used in photocatalytic CO2 reduction, water splitting and other fields. However, the study of COFs in photocatalytic production of H2O2 is still relatively small.
In this paper, based on the mechanism of H2O2 synthesis, the research progress in the field of photocatalytic production of H2O2 by COFs in recent years is summarized. Photocatalytic production of H2O2 usually occurs through the following three Reaction pathways: Oxidation-Reduction Reaction (ORR), Water-Oxidation reaction (WOR), and a dual-channel pathway coupling ORR and WOR. We hope that this paper can provide some reference for researchers in related fields, and promote the development of COFs materials in the field of photocatalytic production of H2O2.

2 Oxygen reduction (ORR) to produce hydrogen peroxide

The production of H2O2 via the photocatalytic oxygen reduction pathway has gradually become a research hotspot[13⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~30]. Compared with traditional photocatalysts, COFs materials have tunable composition and band structure at the molecular and nanoscale levels (Fig. 1), and the photocatalytic performance of COFs materials can be significantly improved by strategies such as element doping, metal loading, and the introduction of active sites.
图1 光催化剂产H2O2的能带结构示意图

Fig. 1 Schematic diagram of band structure of H2O2 production by photocatalyst

Based on the mechanism of photocatalytic oxygen reduction to produce H2O2 and starting from the structural design of COFs, this section will illustrate the research progress of COFs materials in the field of photocatalytic oxygen reduction to produce H2O2 through a series of typical examples.
Two-electron ORR is the most widely studied H2O2 generation pathway in photocatalysis (e.g., Fig. 2). According to the electron transfer process, it can be generally divided into a one-step two-electron path (formula 1) and a two-step one-electron path (formulas 2 to 4).
O2＋2e-＋2H＋→H2O2 E0=+0.68 VNHE
O2＋e-→·O2- E0=-0.33 VNHE
·O2- ＋H＋→*OOH
*OOH ＋H＋＋e-→H2O2 E0 = +1.44 VNHE
e- represents photogenerated electrons; The H+ represents a proton; ·O2- represents superoxide radical; * OOH represents adsorbed OOH radical;
图2 两电子氧还原光催化产过氧化氢示意图

Fig. 2 Schematic diagram of photocatalytic production of hydrogen peroxide by two-electron oxygen reduction

2.1 Direct one-step two-electron oxygen reduction mechanism

Photocatalyzed ORR is a promising strategy for H2O2 synthesis, and the one-step two-electron pathway in particular has great potential in achieving high efficiency and selectivity.
In November 2020, Thomas and Van Der Voort et al. Synthesized two kinds of COFs linked by imine bonds (Figure 3A)[31]. Visible light irradiation forms electron hole carriers on COFs, ethanol uses holes to produce acetaldehyde and protons, and molecular oxygen uses electrons from COF and protons from alcohol conversion to produce H2O2（ Fig. 3 B) with a yield of 91.00~234.52μmol·h-1·g-1. This report is the first time to use COFs materials for oxygen reduction to produce H2O2, which provides a new catalyst option for photocatalytic production of H2O2.
图3 (a) TAPD-(Me)2和TAPD-(OMe)2 COF的合成路线示意图[31]; (b)光催化产H2O2的机理示意图[31]; (c) C-COFs、S-COFs和FS-COFs的合成示意图[32]; (d) C-COFs和FS-COFs氧还原为H2O2的自由能图及FS-COFs生产H2O2的可能步骤[32]

Fig. 3 Schematic diagram of the synthesis route of (a) TAPD-(Me)2 and TAPD-(OMe)2 COF[31]; (b) Schematic diagram of the mechanism of photocatalytic hydrogen peroxide production[31]; (c) Synthesis diagram of C-COFS, S-COFs and FS-COFs[32]; (d) Free energy diagram of reduction of O2 via C-COFs and FS-COFs to H2O2 and possible steps of H2O2 production by FS-COFs[32]

Han et al. Synthesized S-COFs and FS-COFs by introducing sulfone units (Fig. 3C, d)[32]. The simulation results show that FS-COFs form a yeager-type conformation with strong oxygen adsorption ability, which accelerates the separation of photogenerated electron-hole pairs, enhances the protonation of COFs, and promotes the adsorption of O2. Compared with the unmodified C-COFs, the conformational transition changes the path of H2O2 production from two-step one-electron oxygen reduction to one-step two-electron oxygen reduction, and the H2O2 yield reaches 3904.2μmol·h-1·g-1.

2.2 Indirect two-step one-electron oxygen reduction mechanism

At present, there are few reports on the generation of H2O2 through the one-step two-electron ORR pathway, and the mechanism of photocatalytic generation of H2O2 is still focused on the two-step one-electron ORR pathway.
The introduction of metal active sites is an important strategy to regulate the photocatalytic performance of COFs. Jiang et al. Obtained CoPc-BTM-COF and CoPc-DAB-COF by introducing a metal Co atom as the active center of ORR (Fig. 4A)[33]. The formation of the *OOH intermediate species was confirmed and the two-step one-electron oxygen reduction pathway was revealed by electron paramagnetic resonance and in situ infrared spectroscopy (Fig. 4 B – e). The introduction of metal atom active sites greatly promoted the adsorption of oxygen, and the H2O2 yield of CoPc-BTM-COF reached 2096μmol·h-1·g-1. Gu et al. Reported the first 3D-Ti-based COF with spn topology (TiCOF-spn), which has strong visible light absorption ability and exhibits certain H2O2 photocatalytic activity （489.94μmol·g-1·h-1） This study expands the topology of 3D COFs and broadens the application of metal-containing COFs in the field of photocatalytic oxygen reduction to produce H2O2[17]. Although the introduction of metal active sites can improve the photocatalytic performance of COFs to a certain extent, its application is limited due to the high cost of raw materials and the environmental pollution.
图4 (a) CoPc-BTM-COF和CoPc-DAB - COF的合成路径示意图；(b)电子顺磁共振光谱；(c) CoPc-BTM-COF中Co原子和N原子的氧吸附能计算；(d) CoPc-BTM-COF光催化体系的原位红外光谱；(e) CoPc上的2e-(橙色)和4e-(青色)ORR过程的自由能图[33]

Fig. 4 (a) Schematic diagram of synthesis paths of CoPc-BTM-COF and COPc-DAB-COF; (b) EPR spectrum; (c) Calculated oxygen adsorption energy of Co atom and N atom in CoPc-BTM-COF; (d) FT-IR spectra of COPc-BTM-COF photocatalytic systems in situ (e) Free energy diagrams of 2e-(orange) and 4e-(cyan)ORR processes on CoPc[33]

Comparatively speaking, non-metallic active sites have been widely studied because of their controllable catalytic ability and low cost. Gu et al. Rationally designed a covalent organic framework Bpy-TAPT retaining the polar aldehyde group and dual active sites (bipyridine and triazine) (Figure 5A) with a H2O2 yield of 4038μmol·h-1·g-1（ Figure 5B)[34]. Its two-step one-electron oxygen reduction mechanism is shown in Fig. 5 C, d ：h+ oxidizes H2O to O2 at the bipyridine site,e- is reduced at the triazine ring to O2 to produce ·O2-, which is then converted to H2O2 by e- reduction. The introduction of double active sites enhances the charge generation, and the electron-rich aldehyde group effectively promotes the separation of charge carriers and the adsorption of O2/H+.
图5 (a) Bpy-TAPT的合成路线示意图；(b) 三种COFs光催化生产H2O2的研究；(c) Bpy-TAPT和Bpy-TAPB的电子顺磁共振光谱；(d) Bpy-TAPT光催化产H2O2机理[34]

Fig. 5 (a) Schematic diagram of the composite route of Bpy-TAPT; (b) Photocatalytic production of H2O2 by three COFs; (c) EPR spectra of Bpy-TAPT and Bpy-TAPB; (d) Mechanism of H2O2 production by Bpy-TAPT photocatalysis[34]

Alkynyl-modified COFs have attracted much attention in the field of photocatalysis. The COFs constructed by Kong et al. Through strong π − π conjugated polycyclic aromatic benzene and acetylene units have excellent photoresponse performance, and the H2O2 yield is 1240μmol·h-1·g-1[35]. In addition, the research on new active centers of COFs has never stopped. Van Der Voort et al. Prepared COFs containing pyrene structure and explored their photocatalytic performance, and the yield of Van Der Voort was 1242μmol·h-1·g-1[24]. Wang et al. Successfully synthesized three kinds of azole COFs materials, including thiazole, oxazole and imidazole, and constructed a more accessible charge transfer channel through the donor-π-acceptor structure, thus effectively inhibiting the recombination of photoexcited charges[36].
The structural tunability of COFs enables multiple choices of building units. Cooper et al. Have done a lot of work in the structural design and synthesis of COFs, revealing the influence of building units of COFs materials on photocatalytic H2O2[37]. In addition, ligand functionalization is also one of the effective strategies to regulate the properties of COFs. Han et al. Developed a partially fluorinated, metal-free, imine-linked two-dimensional triazine-based covalent organic framework （TF50-COF） photocatalyst[38]. Abundant Lewis acid sites were generated by fluorine substitution to adjust the electron distribution of adjacent carbon atoms, which provided highly active sites for O2 adsorption and broadened the visible light response range of the catalyst, and the H2O2 yield was 1739μmol·h-1·g-1. In addition, they modified COFs materials by cyano groups to form a D-π-A structure, which promoted the adsorption of oxygen and the response to visible light, and significantly improved the charge separation efficiency[39]. The synergistic effect caused by this strategy promoted the activation of O2 from ·O2- to 1O2 under visible light irradiation, and the H2O2 yield reached 2623μmol·h-1·g-1.
Wang et al. Synthesized functionalized TAPB-PDA-X via 1,3,5-tris (4-aminophenyl) benzene and terephthalaldehyde with different functional groups （X=H2,OH,OCH3 and CH3）[40]. The COF modified by hydroxyl functional groups can effectively capture holes and reduce the recombination of photogenerated carriers, and the H2O2 yield reaches 2117.6μmol·g-1·h-1. The ligand functionalization strategy is simple and feasible, which promotes the application of COFs materials in the field of photocatalytic production of H2O2.
Overall, the introduction of metal or non-metal active sites can improve the photocatalytic performance of COFs materials, further affect the process of oxygen adsorption and electron transfer, and ultimately enhance the yield of H2O2. In addition, from the point of view of the material itself, the photocatalytic performance can be greatly improved by the selection of building units and ligand functionalization strategies, which also makes the research of COFs materials in the field of photocatalytic production of H2O2 possible.

3 Water oxidation (WOR) to produce hydrogen peroxide

Compared with ORR, WOR is an alternative pathway for the conversion of H2O to H2O2 using light-induced production of h+. WOR contains the following paths:
2 H2O + 2 h+→ H2O2 + 2 H+, E0= + 1.78 VNHE
H2O + h+→ H+ + ·OH, E0= + 2.732 VNHE
OH- + h+→ ·OH, E0= + 1.9 VNHE
·OH + ·OH→H2O2
h+ represents photogenerated holes; e- represents photogenerated electrons; ·O2- represents superoxide radical; *OOH represents the adsorbed OOH radical; ; OH represents hydroxyl radical; The OH- comes from the ionization of water;
In WOR, the h+ generated by the photoinduced catalyst realizes the direct conversion of H2O to H2O2 through one-step two-electron oxidation (as shown in Equation 5). In addition, it can also indirectly produce H2O2 by two-step one-electron oxidation (such as formula 6~8）：h+ first forms hydroxyl radical with H2O, and then through the coupling of hydroxyl radical. Theoretically, the valence band energy of the catalyst is required to reach 1.78 eV for one-step two-electron oxidation and 2.732 eV for two-step one-electron oxidation.
Yu and Li et al. Designed four isostructural hydrazone-linked COFs using the hydrophilic hydrazone structure as the active site for water oxidation (Figure 6A)[41]. The possible mechanism of WOR process is as follows: the electrons generated by photoexcitation can increase the polarity of the hydrazone bond and promote the hydration of water and hydrazone bond. Upon photoinduced deprotonation, the hydroxyl radical formed directly couples to produce H2O2（ Fig. 6B, C), reaching a yield of 1665μmol·h-1·g-1 in pure water.
图6 （a）COF合成示意图；（b）DETH-COF水氧化反应自由能变化；（c）反应机理示意图[41]

Fig. 6 (a) Synthesis diagram of COF；(b) the free energy change of water oxidation reaction on DETH-COF；(c) Schematic diagram of the reaction mechanism[41]

4 Double-channel hydrogen peroxide production

In most catalytic systems for ORR to produce H2O2, the oxidation potential is too low to realize the WOR process, which leads to the failure of photogenerated holes to be consumed in time, resulting in photogenerated charge recombination, low charge utilization efficiency, and weak H2O2 production performance.
Different from other reaction pathways of photosynthetic H2O2, the two-pass pathway of direct two-electron water oxidation coupled with direct two-electron oxygen reduction can achieve 100% atom utilization and high energy conversion efficiency, so it is urgent to develop polymeric catalysts capable of synthesizing H2O2 through this pathway.
In COFs materials, in order to realize the WOR path, it is an ideal process to control the band structure by designing the structural unit and bonding mode, and then realize the dual-channel path photocatalytic production of H2O2 (Fig. 7).
图7 COF通过双通道光催化产H2O2示意图

Fig. 7 Schematic diagram of COF photocatalytic production of H2O2 through dual channels

Xu et al. First reported the two-channel synthesis of alkynyl-functionalized covalent triazine framework materials H2O2（ as shown in Fig. 8 a, B)[42]. The theoretical calculation results show that the alkynyl structural unit as the active site of WOR can significantly reduce the Gibbs free energy of the hydroxyl intermediate state (Fig. 8C), and the ORR on the coupled triazine unit realizes the two-channel path synthesis H2O2. On this basis, they designed the heptazine ring unit (Figure 8 d) to deepen the oxidation potential of the material[43]. The ORR occurs at the heptazine ring unit, while the WOR occurs at the alkynyl unit, achieving 100% atom utilization efficiency as well as 0.78% solar-to-chemical energy conversion efficiency during the photochemical synthesis of H2O2. Studies have shown that the benzene ring is the active center of WOR[44]. The triazine ring and benzene ring were further integrated onto heptazinyl COF to give HEP-TAPT-COF and HEP-TABB-COF (Fig. 8E)[45]. Comparatively speaking, HEP-TAPT-COF exhibits higher photocatalytic efficiency for H2O2 production due to its dual ORR active sites.
图8 （a）CTFs的化学结构[42]；（b）氧气吸附吉布斯自由能变图[42]；（c）直接两电子水氧化反应路径合成过氧化氢的吉布斯自由能变化图[42];（d）CHFs的化学结构[43]；（e）HEP-TAPT-COF和HEP-TAPB-COF合成示意图[45]

Fig. 8 (a) The chemical structure of CTFs[42]; (b) Oxygen adsorption Gibbs free energy variable map[42]; (c) Direct two-electron water oxidation reaction path synthesis of hydrogen peroxide Gibbs free energy variation[42]; (d) The chemical structure of CHFs[43]; (e) Synthesis diagram of HEP-TAPT-COF and HEP-TAPB-COF[45]

Ma et al. Prepared bipyridyl COF (COF-TfpBpy) from 1,3,5-triformylphloroglucinol (Tfp) and 2,2 ′ -bipyridine-5,5 ′ -diamine (Bpy) (Fig. 9 a ~ e)[46]. In situ infrared measurements, as well as DFT calculations, revealed the mechanism of its two-channel pathway for H2O2 production: under illumination, water molecules undergo one-step two-electron oxidation, leaving two protonated pyridine substituents （PyH+）, and oxygen molecules adsorb on the PyH+ substituent to form an internal peroxide intermediate (N − H − O − O − H − N), which is converted to H2O2 by two-electron reduction, realizing a H2O2 production process with 100% atom utilization efficiency.
图9 （a）联吡啶活性位点合成COF-TfpBpy的示意图；（b）g-C3N4结构示意图（c）和（d）光催化产H2O2过程中的位于900~1650 cm−1和3000~3500 cm−1处的原位红外[46]；（e）光催化产H2O2过程中的位于900~1650 cm−1处的原位红外[46]；（f）TTF-BT-COF的结构[47]；（g）TD-COF和TT-COF的化学结构[48]

Fig. 9 (a) Schematic diagram of the synthesis of COF-TfpByy from the active site of bipyridine (b) g-C3N4 structure (c) and (d) in situ infrared at 900~1650 cm−1 and 3000~3500 cm−1 during photocatalytic production of H2O2 (e) in situ infrared at 900~1650 cm−1 during photocatalytic production of H2O2[46]; (f) The chemical structure of TTF-BT-COF[47]; (g)The chemical structures of TD-COF and TT-COF [48]

These methods have shown excellent performance in photocatalytic production of H2O2, but there is still a long way to go for industrial application. In the actual industrial production, it is often necessary to provide high concentration of H2O2, which requires that the designed COFs materials can maintain high performance to produce H2O2 for a long time. Lan and others have made breakthroughs in this field[47]. TTF-BT-COF (Figure 9 f), with the oxidation group tetrathiafulvalene (TTF) and the reduction group benzothiazole (BT) as the reaction center, has a H2O2 photosynthesis yield of ~276 000μmol·h-1·g-1 without sacrificial agents, and its H2O2 concentration reaches about 18.7 wt% during the long catalytic reaction, which has great industrial application prospects.
Only about 2.5% of global water resources are freshwater resources. Therefore, how to use seawater resources is a research hotspot. Tang et al. Constructed two thiophene-containing covalent organic frameworks (TD-COF and TT-COF) (Figure 9 G), using only seawater and air as reactants, and achieved H2O2 photosynthetic yields of 3364μmol·h-1·g-1 and 2890μmol·h-1·g-1[48]. This provides a new idea for the design of new catalysts for photocatalytic production of H2O2.
The catalytic performance of COFs is not only determined by the chemical structure of their building units, but also can be optimized by constructing highly connected 3D COFs with topological structure. Zhang et al. First designed and synthesized an octaaldehyde difluorophenyl monomer (FBTA-8CHO) as an 8-connected cubic node, which provided more options for the design and construction of various unique 3D COFs and laid the foundation for the efficient preparation of various 3D COFs for photocatalytic production of H2O2[49].
Modification with different functional groups can change the light absorption range of COFs materials, affect the charge distribution of structural units and provide more reactive sites to improve the performance of COFs in photocatalytic H2O2 production. Shen et al. Prepared thioether-modified triazine-based COF (TDB-COF) via Schiff base reaction (Figure 10A)[50]. The experimental results show that compared with TFPT-COF without thioether group modification, the modification of thioether group broadens the visible light absorption range, regulates the band structure which is more conducive to H2O2 production, and reduces the Gibbs free energy of intermediates in WOR process and ORR process (as shown in Fig. 10 B, C), so that TDB-COF shows 723.5μmol·h-1·g-1 H2O2 production without any sacrificial agent or cocatalyst.
图10 （a）基于多组分策略的TDB-COF制备及光催化示意图；（b）WOR路径吉布斯自由能变化；（c）ORR路径吉布斯自由能变化[50]

Fig. 10 (a) Preparation of TDB-COF based on multi- component strategy and photocatalysis schematic diagram; (b) WOR path Gibbs free energy change and (c) ORR path Gibbs free energy change[50]

To sum up, the WOR process can be realized by (1) designing structural units to increase the oxidation potential of COF; (2) designing the "D-A" structure by using the affinity of different units to electrons to improve the separation ability of photogenerated charges; (3) changing the bonding mode to enhance the activity of adjacent units; (4) Introducing functional group modification, changing charge distribution and other strategies to enhance the ability of COF photocatalytic production of H2O2.
Table 1 is a summary of the application of COFs materials to photocatalytic hydrogen peroxide production through the ORR pathway.
表1 COFs材料通过ORR路径应用于光催化产过氧化氢

Table 1 COFs materials are applied to photocatalytic hydrogen peroxide production via ORR path

Photocatalyst Reaction condition Solution condition H2O2 generation rate ref
CTF-NS-5BT λ>420 nm Water:BA (9∶1) 1630 μmol·h-1·gcat-1 13
TPB-DMTP-COF λ > 420 nm Pure water 2882 μmol·h-1·gcat -1 14
TpMa/CN-5 λ>420 nm Isopropanol＋water 880.46 μmol 15
COF-TTA-TTTA λ~420 nm H2O∶EtOH=9∶1 4347 μmol·h-1·gcat-1 16
TiCOF-spn \ \ 489.94 μmol·h-1·gcat-1 17
EBA-COF λ=420 nm H2O∶benzyl alcohol=9∶1 2550 μmol·h-1·gcat-1 18
Bpt-CTF λ=350~780 nm H2O 32.681 μmol/h 19
N0-COF λ=495 nm \ 15.7 μmol/h 20
1H-COF \ \ 18.3 μmol/h 21
TpDz λ>420 nm H2O 7327 umol h-1 gcat-1 22
DMCR-1NH λ = 420~700 nm Water∶IPA (10∶1) 2588 μmol·h-1·gcat-1 23
Py-Da-COF λ >420 nm H2O∶BA = 9∶1 1242 μmol·h-1·gcat-1 24
4PE-N-S λ > 420 nm Real seawater∶EtOH= 9∶1 2556 μmol·h-1·gcat-1 25
PMCR-1 λ= 420~700 nm Water∶BA (10∶1) 129 028 μmol/g (60 h) 26
COF-TpHt λ>420 nm H2O∶BnOH=9∶1 11 986 μmol·h-1·gcat-1 28
TpAQ-COF-12 λ > 420 nm pure water 420 μmol·h-1·gcat-1 29
TAPD-(Me)2-COF λ=420~700nm H2O∶EtOH=1∶9 234.52 μmol·h-1·gcat-1 31
FS-COFs λ > 420 nm H2O 3904 μmol·h-1·gcat-1 32
CoPc-BTM-COF λ>400 nm H2O∶EtOH=9∶1 2096 μmol·h-1·gcat-1 33
Bpy-TAPT λ>420 nm H2O 4038 μmol·h-1·gcat-1 34
COF-TAPB-BPDA λ > 420 nm H2O∶BA (4∶1) 1240 μmol·h-1·gcat-1 35
TZ-COF \ H2O∶Benzyl alcohol (1∶1) 4951 μmol·h-1·gcat-1 36
SonoCOF-F2 λ>420 nm \ 197 μmol(24 h) 37
TF50-COF λ>400 nm H2O∶EtOH=9∶1 1739 μmol·h-1·gcat-1 38
CN-COF λ>400 nm H2O∶EtOH (9∶1) 2623 μmol·h-1·gcat-1 39
TAPB-PDA-OH λ=420 nm H2O∶EtOH=9∶1 2117.6 μmol·h-1·gcat-1 40
Table 2 is a summary of the application of COFs materials to photocatalytic hydrogen peroxide production through WOR and dual-channel pathways.
表2 COFs材料通过WOR和双通道路径应用于光催化产过氧化氢

Table 2 COFs materials used for photocatalytic hydrogen peroxide production via WOR and dual-channel pathways

Photocatalyst Reaction Condition Solution condition H2O2 generation rate Ref
DETH-COF λ=450 nm Pure Water 1665 μmol·g-1·h-1 41
CTF-BDDBN λ>420 nm Pure Water 26.6 μmol·h-1 42
CTF-DPDA λ>420 nm Pure Water 69 μmol·h-1 43
HEP-TAPT-COF λ>420 nm Pure Water 87.50 μmol·h−1 45
COF-TfpBpy λ=420 nm Pure Water 1 042 μM·h−1 46
TTF-BT-COF λ=412 nm Pure Water 276 000 μM·h−1·g−1 47
TD-COF λ>420 nm Sea Water 3 364 μmol·h -1·g-1 48
COF-nust-8 λ>420 nm H2O∶EtOH=9∶1 1 081 μmol·h -1·g-1 49
TDB-COF λ>420 nm Pure Water 723.5 μmol·h -1·g-1 50

5 Conclusion and outlook

Covalent organic frameworks (COFs), as a new type of functional polymer porous materials, have been widely studied in photocatalysis, membrane separation, and other fields because of their advantages such as high specific surface area, regular and diverse structures, controllable structural design, appropriate optical band gap, and high physical and chemical stability. In the field of photocatalysis, it provides a green and environmentally friendly route for the production of H2O2, which meets the needs of the current dual-carbon development strategy.
(1) At present, there are many studies on ORR pathway, but there is a lack of more detailed studies on WOR pathway. Photocatalytic production of H2O2 via the WOR pathway remains difficult. To solve this problem, it is necessary to find new building blocks and linkers, introduce specific active groups, and design new COF materials with deeper oxidation potential to realize the WOR process and improve the photocatalytic performance and atom utilization efficiency of COF.
(2) Photocatalytic production of H2O2 is still a long way from industrial application. The photostability and catalytic stability of the material itself are still the key research contents.
(3) In addition to exploring direct photocatalytic H2O2 production methods, we can also consider the direct use of covalent organic frameworks for photocatalytic H2O2 production and its tandem reactions, such as photocatalytic in situ H2O2 production and its use in organic synthesis, photodynamic therapy, photoenzyme tandem reactions, etc., so that they can efficiently produce and use H2O2 in situ.

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]
Chen Z, Yao D C, Chu C C, Mao S. Chem. Eng. J., 2023, 451: 138489.

[2]
Fu Y J, Liu C A, Zhang M l, Zhu C, Li H, Wang H B, Song Y X, Huang H, Liu Y, Kang Z H. Adv. Energy Mater., 2018, 8: 1802525.

[3]
Liu Y, Zhao Y, Wang J L. J. Hazard. Mater., 2021, 404: 124191.

[4]
Sang Y J, Cao F F, Li W, Zhang L, You Y W, Deng Q Q, Dong K, Ren J S, Qu X G. J. Am. Chem. Soc., 2020, 142(11): 5177.

[5]
Zhao C, Shi C J, Li Q, Wang X Y, Zeng G, Ye S, Jiang B J, Liu J. Mater. Today Energy, 2022, 24: 100926.

[6]
Melchionna M, Fornasiero P, Prato M. Adv. Mater., 2019, 31(13): 1802920.

[7]
Song X. Master’s Dissertation of Yanshan University, 2020.

(宋鑫. 燕山大学硕士论文, 2020)

[8]
Wu M J. Master’s Dissertation of Beijing University of Chemical Technology, 2019.

(吴敏杰. 北京化工大学硕士论文, 2019)

[9]
Fukuzumi S, Lee Y M, Nam W. Chin. J. Catal., 2021, 42(8): 1241.

[10]
Li X L. Master's dissertation of Zhengzhou University, 2020.

(李新立. 郑州大学硕士论文, 2020 )

[11]
Yang X R, Deng M Y, Zhang X X, Applied Chemical Industry, 2023, 52 (5): 1508.

(杨晓茹, 邓明杨, 张晓昕. 应用化工, 2023, 52 (5): 1508.).

[12]
Zhang T, Zhang G, Chen L. Acc. Chem. Res., 2022, 55(6): 795.

[13]
Yu X H, Viengkeo B, He Q, Zhao X, Huang Q L, Li P P, Huang W, Li Y G. Adv. Sustain. Syst., 2021, 5(10): 2100184.

[14]
Li L J, Xu L P, Hu Z F, Yu J C. Adv. Funct. Mater., 2021, 31: 2106120.

[15]
Wang H, Almatrafi E, Wang Z W, Yang Y, Xiong T, Yu H B, Qin H, Yang H L, He Y Z, Zhou C Y, Zeng G M, Xu P. J. Colloid Interface Sci., 2022, 608: 1051.

[16]
Tan F L, Zheng Y Y, Zhou Z P, Wang H L, Dong X, Yang J, Ou Z W, Qi H Y, Liu W, Zheng Z K, Chen X D. CCS Chem., 2022, 4(12): 3751.

[17]
Han W K, Lu H S, Fu J X, Liu X, Zhu X M, Yan X D, Zhang J W, Jiang Y Q, Dong H L, Gu Z G. Chem. Eng. J., 2022, 449: 137802.

[18]
Zhai L P, Xie Z P, Cui C X, Yang X B, Xu Q, Ke X T, Liu M H, Qu L B, Chen X, Mi L W. Chem. Mater., 2022, 34(11): 5232.

[19]
Wu C B, Teng Z Y, Yang C, Chen F S, Yang H B, Wang L, Xu H X, Liu B, Zheng G F, Han Q. Adv. Mater., 2022, 34: 2110266.

[20]
Chai S M, Chen X W, Zhang X R, Fang Y X, Sprick R S, Chen X. Environ. Sci. Nano, 2022, 9(7): 2464.

[21]
Hu H, Tao Y L, Wang D, Li C L, Jiang Q C, Shi Y X, Wang J, Qin J P, Zhou S J, Kong Y. J. Colloid Interface Sci., 2023, 629: 750.

[22]
Liao Q, Sun Q, Xu H, Wang Y, Xu Y, Li Z, Hu J, Wang D, Li H, Xi K. Angew. Chem. Int. Ed., 2023, e202310556.

[23]
Das P, Chakraborty G, Roeser J, Vogl S, Rabeah J, Thomas A. J. Am. Chem. Soc., 2023, 145(5): 2975.

[24]
Sun J M, Sekhar Jena H, Krishnaraj C, Singh Rawat K, Abednatanzi S, Chakraborty J, Laemont A, Liu W L, Chen H, Liu Y Y, Leus K, Vrielinck H, Van Speybroeck V, Van Der Voort P. Angew. Chem. Int. Ed., 2023, 62(19): 2216719.

[25]
Deng M J, Sun J M, Laemont A, Liu C H, Wang L Y, Bourda L, Chakraborty J, Van Hecke K, Morent R, De Geyter N, Leus K, Chen H, Van Der Voort P. Green Chem., 2023, 25(8): 3069.

[26]
Das P, Roeser J, Thomas A. Angew. Chem. Int. Ed., 2023, 62(29): 2304349.

[27]
Yang S, Lu L L, Li J, Cheng Q Q, Mei B B, Li X W, Mao J N, Qiao P Z, Sun F F, Ma J Y, Xu Q, Jiang Z. SusMat, 2023, 3(3): 379.

[28]
Shao C C, He Q, Zhang M C, Jia L, Ji Y J, Hu Y P, Li Y Y, Huang W, Li Y G. Chin. J. Catal., 2023, 46: 28.

[29]
Zhang X C, Zhang J Z, Miao J, Wen X, Chen C, Zhou B X, Long M C. Chem. Eng. J., 2023, 466: 143085.

[30]
Trenker S, Grunenberg L, Banerjee T, Savasci G, Poller L M, Muggli K I M, Haase F, Ochsenfeld C, Lotsch B V. Chem. Sci., 2021, 12(45): 15143.

[31]
Krishnaraj C, Sekhar Jena H, Bourda L, Laemont A, Pachfule P, Roeser J, Chandran C V, Borgmans S, Rogge S M J, Leus K, Stevens C V, Martens J A, Van Speybroeck V, Breynaert E, Thomas A, Van Der Voort P. J. Am. Chem. Soc., 2020, 142(47): 20107.

[32]
Luo Y, Zhang B P, Liu C C, Xia D H, Ou X W, Cai Y P, Zhou Y, Jiang J, Han B. Angew. Chem. Int. Ed., 2023, 62(26): 2305355.

[33]
Zhi Q J, Liu W P, Jiang R, Zhan X N, Jin Y C, Chen X, Yang X Y, Wang K, Cao W, Qi D D, Jiang J Z. J. Am. Chem. Soc., 2022, 144(46): 21328.

[34]
Liu Y, Han W K, Chi W W, Mao Y Q, Jiang Y Q, Yan X D, Gu Z G. Appl. Catal. B Environ., 2023, 331: 122691.

[35]
Yang T, Chen Y, Wang Y C, Peng X Q, Kong A G. ACS Appl. Mater. Interfaces, 2023, 15(6): 8066.

[36]
Mou Y, Wu X D, Qin C C, Chen J Y, Zhao Y L, Jiang L B, Zhang C, Yuan X Z, Huixiang Ang E, Wang H, Angew. Chem. Int. Ed., 2023, e202309480.

[37]
Zhao W, Yan P Y, Li B Y, Bahri M, Liu L J, Zhou X, Clowes R, Browning N D, Wu Y, Ward J W, Cooper A I. J. Am. Chem. Soc., 2022, 144(22): 9902.

[38]
Wang H Z, Yang C, Chen F S, Zheng G F, Han Q. Angew. Chem. Int. Ed., 2022, 61: e202202328.

[39]
Di X, Lv X M, Wang H Z, Chen F S, Wang S Y, Zheng G F, Wang B, Han Q. Chem. Eng. J., 2023, 455: 140124.

[40]
Yang Y P, Kang J X, Li Y, Liang J J, Liang J X, Jiang L, Chen D M, He J, Chen Y J, Wang J Q. New J. Chem., 2022, 46(45): 21605.

[41]
Pan G D, Hou X S, Liu Z Y, Yang C K, Long J L, Huang G C, Bi J H, Yu Y, Li L Y. ACS Catal., 2022, 12(24): 14911.

[42].
Chen L, Wang L, Wan Y Y, Zhang Y, Qi Z M, Wu X J, Xu H X. Adv. Mater., 2020, 32: 1904433.

[43].
Cheng H, Lv H F, Cheng J, Wang L, Wu X J, Xu H X. Adv. Mater., 2022, 34: 2107480.

[44]
Wan Y Y, Wang L, Xu H X, Wu X J, Yang J L. J. Am. Chem. Soc., 2020, 142(9): 4508.

[45]
Chen D, Chen W B, Wu Y T, Wang L, Wu X J, Xu H X, Chen L. Angew. Chem. Int. Ed., 2023, 62(9): 2217479.

[46]
Kou M P, Wang Y Y, Xu Y X, Ye L Q, Huang Y P, Jia B H, Li H, Ren J Q, Deng Y, Chen J H, Zhou Y, Lei K, Wang L, Liu W, Huang H W, Ma T Y. Angew. Chem. Int. Ed., 2022, 61(19): 2200413.

[47]
Chang J N, Li Q, Shi J W, Zhang M, Zhang L, Li S, Chen Y F, Li S L, Lan Y Q. Angew. Chem. Int. Ed., 2023, 62(9): 2218868.

[48]
Yue J Y, Song L P, Fan Y F, Pan Z X, Yang P, Ma Y, Xu Q, Tang B. Angew. Chem. Int. Ed., 2023, 62(38): 2309624.

[49]
Wu M M, Shan Z, Wang J J, Liu T T, Zhang G. Chem. Eng. J., 2023, 454: 140121.

[50]
Zhou Z M, Sun M H, Zhu Y B, Li P Z, Zhang Y R, Wang M K, Shen Y. Appl. Catal. B Environ., 2023, 334: 122862.

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