基于阳极甘油氧化电催化的碱/酸混合电解制氢研究

doi:10.13208/j.electrochem.2215005

电化学（中英文） ›› 2023, Vol. 29 ›› Issue (2): 2215005. doi: 10.13208/j.electrochem.2215005

所属专题： “电催化和燃料电池”专题文章

基于阳极甘油氧化电催化的碱/酸混合电解制氢研究

冯辛^a^,^b, 刘博文^a, 郭可鑫^a, 范林丰^b, 王根香^b, 次素琴^a^,^*(), 温珍海^b^,^*()

^a南昌航空大学，江西省持久性污染物控制与资源循环利用重点实验室，江西南昌 330063
^b中国科学院福建物质结构研究所，中科院功能纳米结构设计与组装重点实验室，福建省纳米材料重点实验室，福建福州，350002

收稿日期:2022-06-01 修回日期:2022-06-23 接受日期:2022-08-29 出版日期:2023-02-28 发布日期:2022-08-31

Anodic Electrocatalysis of Glycerol Oxidation for Hybrid Alkali/Acid Electrolytic Hydrogen Generation

Xin Feng^a^,^b, Bo-Wen Liu^a, Ke-Xin Guo^a, Lin-Feng Fan^b, Gen-Xiang Wang^b, Su-Qin Ci^a^,^*(), Zhen-Hai Wen^b^,^*()

^aKey Laboratory of Jiangxi Province for Persistent Pollutants Control, National-Local Joint Engineering Research Center of Heavy Metals Pollutants Control and Resource Utilization and Resources Recycle, Nanchang Hangkong University, Nanchang, 330063, Jiangxi, China
^bCAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China

Received:2022-06-01 Revised:2022-06-23 Accepted:2022-08-29 Published:2023-02-28 Online:2022-08-31
Contact: ^*Su-Qin Ci, Tel: (86-791) 83953378, E-mail address: sqci@nchu.edu.cn.; ^*Zhen-Hai Wen, Tel: (86-591) 6317353, E-mail address: wen@fjirsm.ac.cn

1. 2215005.pdf(507KB)

摘要/Abstract

摘要：

耦合可再生电能的电解水制氢是一项极具前景的绿氢技术，该技术仍受限于阳极析氧反应（OER）动力学慢、过电位高等问题的限制。在阳极端采用热力学更容易的电氧化反应代替OER，可大幅降低电耗并且在阳极端获得增值产物，是电解制氢的一种新策略。甘油作为生物柴油生产的主要副产品且产能过剩，其电催化氧化（GOR）理论电位比OER低。基于此，本研究工作报道了一种耦合酸性析氢反应（HER）与碱性GOR的混合酸/碱双电解液的制氢电解器，其以泡沫镍（NF）支撑Co₃O₄纳米片（NS）电极（Co₃O₄·NSs/NF）为阳极，商用碳载铂修饰碳布电极为阴极。在阳极端，Co₃O₄·NSs/NF对GOR电催化表现出较低的过电位和转化为甲酸盐的高选择性。在该混合酸/碱双电解液电解槽中，仅仅需要额外施加0.55 V的外加电压，即可达到10 mA·cm^-2的产氢电解电流密度，并可以在阳极将甘油高选择性地转化为甲酸盐，其中产氢的法拉第效率接近100%。本研究工作为电解制氢提供了一条节电、阳极增值转化的技术路线。

关键词: 自支撑电极, 甘油电氧化, 电催化, 酸/碱双电解液电解, 制氢

Abstract:

Electrolytic hydrogen production is heavily restricted by high-energy consumption majorly due to the relatively high potential of anodic oxygen evolution reaction (OER). Development of OER-alternative reaction at the anode has been recently proposed as a promising pathway to address the associated issues. In this work, we report a hybrid acid/alkali dual-electrolyte electrolyzer by coupling acidic hydrogen evolution reaction (HER) using commercial Pt/C cathode with alkaline electrocatalytic glycerol oxidation (GOR) which is implemented by developing a nickel foam (NF) supporting Co₃O₄ nanosheets anode that shows low overpotential and high selectivity toward GOR for formate production. The hybrid acid/alkali electrolyzer only requires an applied voltage of 0.55 V to achieve the electrolytic current density of 10 mA·cm^-2 for glycerol conversion into formate at the anode and H₂ production at the cathode with the Faraday efficiency of about 100%. The present work may open a new avenue to maximize the electron utilization efficiency and implement the energy-saving green route for H₂ generation.

Key words: Self-supporting electrode, Glycerol oxidation, Electrocatalysis, Acid/alkali dual-electrolyte electrolyzer, Hydrogen generation

冯辛, 刘博文, 郭可鑫, 范林丰, 王根香, 次素琴, 温珍海. 基于阳极甘油氧化电催化的碱/酸混合电解制氢研究[J]. 电化学（中英文）, 2023, 29(2): 2215005.

Xin Feng, Bo-Wen Liu, Ke-Xin Guo, Lin-Feng Fan, Gen-Xiang Wang, Su-Qin Ci, Zhen-Hai Wen. Anodic Electrocatalysis of Glycerol Oxidation for Hybrid Alkali/Acid Electrolytic Hydrogen Generation[J]. Journal of Electrochemistry, 2023, 29(2): 2215005.

图/表 4

参考文献 37

[1]	Rahman M Z, Kibria M G, Mullins C B. Metal-free photocatalysts for hydrogen evolution[J]. Chem. Soc. Rev., 2020, 49(6): 1887-1931. doi: 10.1039/c9cs00313d pmid: 32101197
[2]	Li Z S, Li B L, Peng S H, Li D H, Yang S Y, Fang Y P. Novel visible light-induced g-C₃N₄ quantum dot/BiPO₄ nanocrystal composite photocatalysts for efficient degradation of methyl orange[J]. RSC Adv., 2014, 4(66): 35144-35148. doi: 10.1039/C4RA05749J URL
[3]	Navarro R M, Pena M A, Fierro J L G. Hydrogen production reactions from carbon feedstocks: Fossil fuels and biomass[J]. Chem. Rev., 2007, 107(10): 3952-3991. pmid: 17715983
[4]	Li X M, Hao X G, Abudula A, Guan G Q. Nanostructured catalysts for electrochemical water splitting: current state and prospects[J]. J. Mater. Chem., 2016, 4(31): 11973-12000.
[5]	He L Q, Zhang W B, Mo Q J, Huang W J, Yang L C, Gao Q S. Molybdenum carbide-oxide heterostructures: In situ surface reconfiguration toward efficient electrocatalytic hydrogen evolution[J]. Angew. Chem. Int. Ed., 2020, 59(9): 3544-3548. doi: 10.1002/anie.v59.9 URL
[6]	Zhu J, Hu L S, Zhao P X, Lee L Y S, Wong K Y. Recent advances in electrocatalytic hydrogen evolution using nanoparticles[J]. Chem. Rev., 2020, 120(2): 851-918. doi: 10.1021/acs.chemrev.9b00248 pmid: 31657904
[7]	Mallouk T E. Water electrolysis: Divide and conquer[J]. Nat. Chem., 2013, 5(5): 362-363. doi: 10.1038/nchem.1634 pmid: 23609082
[8]	Li X R, Wang C L, Xue H G, Pang H, Xu Q. Electrocatalysts optimized with nitrogen coordination for high-performance oxygen evolution reaction[J]. Coord. Chem. Rev., 2020, 422: 213468. doi: 10.1016/j.ccr.2020.213468 URL
[9]	Xu Q C, Jiang H, Duan X Z, Jiang Z, Hu Y J, Boettcher S W, Zhang W Y, Guo S J, Li C Z. Fluorination-enabled reconstruction of nife electrocatalysts for efficient water oxidation[J]. Nano Lett., 2021, 21(1): 492-499. doi: 10.1021/acs.nanolett.0c03950 pmid: 33258608
[10]	Cao S S, Qi J D, Lei F C, Wei Z M, Lou S S, Yang X Y, Guo Y Q, Hao P, Xie J F, Tang B. Reduction-induced surface reconstruction to fabricate cobalt hydroxide/molybdenum oxide hybrid nanosheets for promoted oxygen evolution reaction[J]. Chem. Eng. J., 2021, 413: 127540. doi: 10.1016/j.cej.2020.127540 URL
[11]	Lu S L, Zhao B, Chen M X, Wang L, Fu X Z, Luo J L. Electrolysis of waste water containing aniline to produce polyaniline and hydrogen with low energy consumption[J]. Int. J. Hydrogen Energy, 2020, 45(43): 22419-22426. doi: 10.1016/j.ijhydene.2020.06.116 URL
[12]	Ding Y, Xue Q, Hong Q L, Li F M, Jiang Y C, Li S N, Chen Y. Hydrogen and potassium acetate Co-production from electrochemical reforming of ethanol at ultrathin cobalt sulfide nanosheets on nickel foam[J]. ACS Appl. Mater. Interfaces, 2021, 13(3): 4026-4033. doi: 10.1021/acsami.0c20554 URL
[13]	Sun F C, Zhou Y, You Z H, Xia H H, Tuo Y X, Wang S T, Jia C P, Zhang J. Bi-functional Fe₃O₄/Au/CoFe-LDH sandwich-structured electrocatalyst for asymmetrical electrolyzer with low operation voltage[J]. Small, 2021: e2103307.
[14]	Duan Y J, Liu Z L, Zhao B, Liu J H. Raspberry-like Pd₃Pb alloy nanoparticles: Superior electrocatalytic activity for ethylene glycol and glycerol oxidation[J]. RSC Adv., 2020, 10(27): 15769-15774. doi: 10.1039/D0RA00564A URL
[15]	Zheng D D, Li J W, Ci S Q, Cai P W, Ding Y C, Zhang M T, Wen Z H. Three-birds-with-one-stone electrolysis for energy-efficiency production of gluconate and hydrogen[J]. Appl. Catal., B, 2020, 277: 119178. doi: 10.1016/j.apcatb.2020.119178 URL
[16]	Kim H J, Kim Y, Lee D E, Kim J R, Chae H J, Jeong S Y, Kim B S, Lee J, Huber G W, Byun J, Kim S, Han J. Coproducing value-added chemicals and hydrogen with electrocatalytic glycerol oxidation technology: Experimental and techno-economic investigations[J]. ACS Sustain. Chem. Eng., 2017, 5(8): 6626-6634. doi: 10.1021/acssuschemeng.7b00868 URL
[17]	Pagliaro M, Ciriminna R, Kimura H, Rossi M, Della Pina C. From glycerol to value-added products[J]. Angew. Chem. Int. Ed., 2007, 46(24): 4434-4440. doi: 10.1002/(ISSN)1521-3773 URL
[18]	Park Y J, Yang J W. Glycerol conversion to high-value chemicals: The implication of unnatural α-amino acid syntheses using natural resources[J]. Green Chem., 2019, 21(10): 2615-2620. doi: 10.1039/c9gc00755e
[19]	Chen Y X, Lavacchi A, Miller H A, Bevilacqua M, Filippi J, Innocenti M, Marchionni A, Oberhauser W, Wang L, Vizza F. Nanotechnology makes biomass electrolysis more energy efficient than water electrolysis[J]. Nat. Commun., 2014, 5: 4036. doi: 10.1038/ncomms5036 pmid: 24892771
[20]	Behr A, Eilting J, Irawadi K, Leschinski J, Lindner F. Improved utilisation of renewable resources: New important derivatives of glycerol[J]. Green Chem., 2008, 10(1): 13-30. doi: 10.1039/B710561D URL
[21]	Anitha M, Kamarudin S K, Kofli N T. The potential of glycerol as a value-added commodity[J]. Chem. Eng. J., 2016, 295: 119-130. doi: 10.1016/j.cej.2016.03.012 URL
[22]	Dodekatos G, Schünemann S, Tüysüz H. Recent advances in thermo-, photo-, and electrocatalytic glycerol oxidation[J]. ACS Catal., 2018, 8(7): 6301-6333. doi: 10.1021/acscatal.8b01317 URL
[23]	Bozell J J, Petersen G R. Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited[J]. Green Chem., 2010, 12(4): 539-554. doi: 10.1039/b922014c URL
[24]	Fan L F, Liu B W, Liu X, Senthilkumar N, Wang G X, Wen Z H. Recent progress in electrocatalytic glycerol oxidation[J]. Energy Technol., 2020, 9(2): 2000804. doi: 10.1002/ente.v9.2 URL
[25]	Huang L, Sun J Y, Cao S H, Zhan M, Ni Z R, Sun H J, Chen Z, Zhou Z Y, Sorte E G, Tong Y Y J, Sun S G. Combined EC-NMR and in situ FTIR spectroscopic studies of glycerol electrooxidation on Pt/C, PtRu/C, and PtRh/C[J]. ACS Catal., 2016, 6(11): 7686-7695. doi: 10.1021/acscatal.6b02097 URL
[26]	Liu Y F, Yu W J, Raciti D, Gracias D H, Wang C. Electrocatalytic oxidation of glycerol on platinum[J]. J. Phys. Chem. C, 2018, 123(1): 426-432. doi: 10.1021/acs.jpcc.8b08547 URL
[27]	Lee S, Kim H J, Lim E J, Kim Y, Noh Y, Huber G W, Kim W B. Highly selective transformation of glycerol to dihydroxyacetone without using oxidants by a PtSb/C-catalyzed electrooxidation process[J]. Green Chem., 2016, 18(9): 2877-2887. doi: 10.1039/C5GC02865E URL
[28]	Tang S S, Li X G, Courté M, Peng J J, Fichou D. Hierarchical Cu(OH)₂@Co(OH)₂Nanotrees for water oxidation electrolysis[J]. ChemCatChem, 2020, 12(16): 4038-4043. doi: 10.1002/cctc.v12.16 URL
[29]	Lv J J, Wang L M, Li R S, Zhang K Y, Zhao D F, Li Y Q, Li X J, Huang X B, Wang G. Constructing a hetero-interface composed of oxygen vacancy-enriched Co₃O₄ and crystalline-amorphous NiFe-LDH for oxygen evolution reaction[J]. ACS Catal., 2021, 11(23): 14338-14351. doi: 10.1021/acscatal.1c03960 URL
[30]	Kou Y, Liu J, Li Y B, Qu S X, Ma C, Song Z S, Han X P, Deng Y D, Hu W B, Zhong C. Electrochemical oxidation of chlorine-doped Co(OH)₂ nanosheet arrays on carbon cloth as a bifunctional oxygen electrode[J]. ACS Appl. Mater. Interfaces, 2018, 10(1): 796-805. doi: 10.1021/acsami.7b17002 URL
[31]	Ray C, Lee S C, Jin B J, Kundu A, Park J H, Jun S C. Conceptual design of three-dimensional CoN/Ni₃N-coupled nanograsses integrated on N-doped carbon to serve as efficient and robust water splitting electrocatalysts[J]. J. Mater. Chem. A, 2018, 6(10): 4466-4476. doi: 10.1039/C7TA10933D URL
[32]	Fan L F, Ji Y X, Wang G X, Chen J X, Chen K, Liu X, Wen Z H. High entropy alloy electrocatalytic electrode toward alkaline glycerol valorization coupling with acidic hydrogen production[J]. J. Am. Chem. Soc., 2022, 144(16): 7224-7235. doi: 10.1021/jacs.1c13740 pmid: 35404594
[33]	Ding Y C, Cai P W, Wen Z H. Electrochemical neutralization energy: from concept to devices[J]. Chem. Soc. Rev., 2021, 50(3): 1495-1511. doi: 10.1039/d0cs01239d pmid: 33346772
[34]	Wang G X, Chen J X, Li K K, Huang J H, Huang Y C, Liu Y J, Hu X, Zhao B S, Yi L C, Jones T W, Wen Z H. Cost-effective and durable electrocatalysts for Co-electrolysis of CO₂conversion and glycerol upgrading[J]. Nano Energy, 2022, 92: 106751. doi: 10.1016/j.nanoen.2021.106751 URL
[35]	Xu Y, Liu M Y, Wang S Q, Ren K L, Wang M Z, Wang Z Q, Li X N, Wang L, Wang H J. Integrating electrocatalytic hydrogen generation with selective oxidation of glycerol to formate over bifunctional nitrogen-doped carbon coated nickel-molybdenum-nitrogen nanowire arrays[J]. Appl. Catal., B, 2021, 298: 120493. doi: 10.1016/j.apcatb.2021.120493 URL
[36]	Vo T G, Ho P Y, Chiang C Y. Operando mechanistic studies of selective oxidation of glycerol to dihydroxyacetone over amorphous cobalt oxide[J]. Appl. Catal. B, 2022, 300: 120723. doi: 10.1016/j.apcatb.2021.120723 URL
[37]	Xie Y A, Zhou Z Y, Yang N J, Zhao G H. An overall reaction integrated with highly selective oxidation of 5‐hydroxymethylfurfural and efficient hydrogen evolution[J]. Adv. Funct. Mater., 2021, 31(34): 2102886. doi: 10.1002/adfm.v31.34 URL

基于阳极甘油氧化电催化的碱/酸混合电解制氢研究

Anodic Electrocatalysis of Glycerol Oxidation for Hybrid Alkali/Acid Electrolytic Hydrogen Generation

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