过氧化氢生产与利用的新进展

doi:10.1016/S1872-2067(20)63767-6

催化学报 ›› 2021, Vol. 42 ›› Issue (8): 1241-1252.DOI: 10.1016/S1872-2067(20)63767-6

过氧化氢生产与利用的新进展

Shunichi Fukuzumi^a^,^b^,^*(), Yong-Min Lee^a^,^c^,^#(), Wonwoo Nam^a^,^$()

^a梨花女子大学化学与纳米科学系, 首尔, 韩国
^b美珠大学科学与工程研究生院, 名古屋, 日本
^c梨花女子大学基础科学研究院, 首尔, 韩国

收稿日期:2020-12-22 接受日期:2021-01-22 出版日期:2021-08-18 发布日期:2021-03-18
通讯作者: Shunichi Fukuzumi,Yong-Min Lee,Wonwoo Nam
作者简介:^$电子信箱：E-mail: wwnam@ewha.ac.kr
^#电子信箱：E-mail: yomlee@ewha.ackr
^*电子信箱：E-mail: fukuzumi@chem.eng.osaka-u.ac.jp

Recent progress in production and usage of hydrogen peroxide

Shunichi Fukuzumi^a^,^b^,^*(), Yong-Min Lee^a^,^c^,^#(), Wonwoo Nam^a^,^$()

^aDepartment of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea
^bGraduate School of Science and Engineering, Meijo University, Nagoya, Aichi 468-8502, Japan
^cResearch Institute for Basic Sciences, Ewha Womans University, Seoul 03760, Korea

Received:2020-12-22 Accepted:2021-01-22 Online:2021-08-18 Published:2021-03-18
Contact: Shunichi Fukuzumi,Yong-Min Lee,Wonwoo Nam
About author:^$. E-mail: wwnam@ewha.ac.kr
^#. E-mail: yomlee@ewha.ackr
^*. E-mail: fukuzumi@chem.eng.osaka-u.ac.jp
Supported by:
This work was supported by the JSPS KAKENHI (16H02268) from MEXT, Japan and by the CRI(2012R1A3A2048842);Basic Science Research Program through NRF of Korea(NRF-2020R1I1A1A01074630)

摘要/Abstract

摘要：

过氧化氢既可用作环境友好的绿色氧化剂, 也可用作燃料电池中的太阳能燃料, 因而受到越来越多的关注. 本文综述了太阳能驱动分子氧氧化水制备过氧化氢及其作为绿色氧化剂和燃料的研究进展. 利用太阳能将水的2e ^‒和4e ^‒氧化与分子氧的2e ^‒还原相结合, 使光催化生产过氧化氢成为可能; 本文讨论了与2e ^‒和4e ^‒水氧化选择性及2e ^‒和4e ^‒氧还原选择性相关的催化反应控制. 由于光催化2e ^‒氧化水和2e ^‒还原分子氧的过程都产生过氧化氢, 因此该组合的催化效率较高. 太阳能光驱动水氧化及分子氧还原生产过氧化氢与过氧化氢催化氧化底物相结合, 在该过程中分子氧用作最环保的氧化剂.

关键词: 过氧化氢生产, 水氧化, 分子氧还原, 光催化氧化, 反应动力学与机理

Abstract:

Hydrogen peroxide has attracted increasing interest as an environmentally benign and green oxidant that can also be used as a solar fuel in fuel cells. This review focuses on recent progress in production of hydrogen peroxide by solar-light-driven oxidation of water by dioxygen and its usage as a green oxidant and fuel. The photocatalytic production of hydrogen peroxide is made possible by combining the 2e– and 4e– oxidation of water with the 2e– reduction of dioxygen using solar energy. The catalytic control of the selectivity of the 2e– vs. 4e– oxidation of water is discussed together with the selectivity of the 2e– vs. 4e– reduction of dioxygen. The combination of the photocatalytic 2e– oxidation of water and the 2e– reduction of dioxygen provides the best efficiency because both processes afford hydrogen peroxide. The solar-light-driven hydrogen peroxide production by oxidation of water and by reduction of dioxygen is combined with the catalytic oxidation of substrates with hydrogen peroxides, in which dioxygen is used as the greenest oxidant.

Key words: Hydrogen peroxide production, Water oxidation, Dioxygen reduction, Photocatalytic oxygenation, Reaction kinetics and mechanism

Shunichi Fukuzumi, Yong-Min Lee, Wonwoo Nam. 过氧化氢生产与利用的新进展[J]. 催化学报, 2021, 42(8): 1241-1252.

Shunichi Fukuzumi, Yong-Min Lee, Wonwoo Nam. Recent progress in production and usage of hydrogen peroxide[J]. Chinese Journal of Catalysis, 2021, 42(8): 1241-1252.

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图/表 17

Fig. 1. (a) Time profiles of photodriven H2O2 production under illumination (λ > 420 nm) of an O2-saturated aqueous solution containing [RuII(4,7-Me2phen)3]2+ (0.20 mM), ScIII(NO3)3 (0.10 M) and NiFe2O4 NPs (0.17 g/L) with diameters of 1300 (black), 120 (blue) and 91 nm (red); (b) Time profile of photodriven H2O2 production under illumination (λ > 420 nm) of an O2-saturated aqueous solution containing Ru(II) (0.20 mM), ScIII(NO3)3 (0.10 M) and NiFe2O4 NPs (0.17 g/L). Ru(II) complex was added to the reaction solution at 50 and 100 h during the visible-light-driven H2O2 production. Reproduced from Ref. [66] with permission from Royal Society of Chemistry (Copyright 2015).

Scheme 1. Photodriven 4e- H2O oxidation combined with 2e- O2 reduction to produce H2O2 with WOC and [Ru(4,7-Me2phen)3]2+ as a photocatalyst. Reproduced from Ref. [50] with permission from Royal Society of Chemistry (Copyright 2013).

Scheme 2. Photocatalytic cycle of photodriven H2O2 production by oxidation of H2O by O2 with Ni(II)[Ru(II)(CN)4(bpy)]. Reproduced from Ref. [68] with permission from Royal Society of Chemistry (Copyright 2017).

Fig. 2. A two-compartment cell employed for photocatalytic H2O2 production by combining the photocatalytic H2O oxidation and the photocatalytic 2e-/2H+ O2 reduction under visible light illumination. Reproduced from Ref. [69] with permission from Royal Society of Chemistry (Copyright 2016).

Scheme 4. Solar-light-driven H2O2 production with FeO(OH)/ BiVO4/FTO photoanode and CoII(Ch)/CP cathode in water or seawater under simulated 1 sun (AM 1.5G) irradiation. Reproduced from Ref. [79] with permission from American Chemical Society (Copyright 2016).

Scheme 5. (a) Three-dimensional structure; (b) Electronic band structure of g-C3N4/PDI (containing 51% PDI unit); (c) Photocatalytic cycle for H2O2 production from H2O and O2 with g-C3N4/PDI. Reproduced from Ref. [98] with permission from American Chemical Society (Copyright 2016).

Fig. 3. (A) Photoanode and cathode for photoelectrochemical water splitting to H2O2 and H2. (B) Energy diagram of photoelectrocatalytic production of H2O2 and H2 using a WO3/BiVO4 photoanode under solar-light illumination. Reproduced from Ref. [110] with permission from Royal Society of Chemistry (Copyright 2016).

Scheme 6. Proposed mechanism of the photocatalytic oxidation of H2O by DDQ with [(N4Py)FeII]2+ to evolve O2. Reproduced from Ref. [102] with permission from American Chemical Society (Copyright 2019).

Scheme 7. A membraneless one-compartment H2O2 fuel cell in which the anode (2e-/2H+ H2O2 oxidation) and cathode (2e-/2H+ H2O2 reduction) reactions afford the output potential of 1.09 V. Reproduced from Ref. [113] with permission from Royal Society of Chemistry (Copyright 2015).

Fig. 4. A photoelectrode system for production of H2O2 via the 2e-/2H+ H2O oxidation on a WO3/BiVO4 photoanode combined with the 2e-/2H+ O2 reduction on an Au cathode under solar-light illumination. Reproduced from Ref. [111] with permission from John WILEY and Sons (Copyright 2017).

Fig. 5. (A) Reaction diagram of photocatalytic production of H2O2; (B) Composite electrode supported WO3/BiVO4 and Au on a single FTO substrate; (C) Solar-light-driven production of H2O2 on the composite electrode under simulated solar-light illumination in H2O containing KHCO3 (2.0 M) at below 5 °C under O2 and CO2 bubbling with use of a petri dish as a cell; (D) Reaction diagram of photocatalytic production of H2O2 on an Au-supported BiVO4 powder in H2O containing KHCO3 (2.0 M) under O2 and CO2 bubbling. Reproduced from Ref. [111] with permission from John WILEY and Sons (Copyright 2017).

Fig. 6. Plots of I-V (blue) and I-P (red) of a one-compartment H2O2 fuel cell with a FeII3[CoIII(CN)6]2/carbon cloth cathode and a Ni mesh anode. Performance tests were carried out in a pH 1.3 aqueous solution, which was transferred from the CoII(Ch)/CP cathode cell of the two- compartment cells containing 52 mM of H2O2 produced by photocatalytic H2O oxidation by O2 (see also Scheme 4). Reproduced from Ref. [79] with permission from American Chemical Society (Copyright 2016).

Scheme 8. Proposed mechanism of photocatalytic hydroxylation of benzene by combining photodriven production of H2O2 via 4e-/4H+ H2O oxidation and 2e-/2H+ O2 reduction with benzene hydroxylation by H2O2 using [RuII(4,7-Me2phen)3]2+ as a photocatalyst and [(Cp*)CoIII(bpy)(H2O)]2+ as a dual function catalyst for the 4e-/4H+ oxidation of water and hydroxylation of benzene. Reproduced from Ref. [129] with permission from Royal Society of Chemistry (Copyright 2017).

Scheme 9. Coupling of photo- and thermal catalysis by FeII2[RuII(CN)6]@sAl-MCM-41 for photocatalytic hydroxylation of benzene by O2 with H2O. Reproduced from Ref. [133] with permission from American Chemical Society (Copyright 2016).

Fig. 8. External bias-free, PEC H2O2 production by oxidation of H2O by O2 with use of an FeOOH/BiVO4/CIGS solar cell in tandem and CN/rGO film electrode under photoirradiation for chemo- and stereospecific conversion of ethylbenzene to obtain (R)-1-phenylethanol catalyzed by AaeUPO. Reproduced from Ref. [134] with permission from American Chemical Society (Copyright 2019).

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过氧化氢生产与利用的新进展

Recent progress in production and usage of hydrogen peroxide

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