基于阳极甘油氧化电催化的碱/酸混合电解制氢研究
收稿日期: 2022-06-01
修回日期: 2022-06-23
录用日期: 2022-08-29
网络出版日期: 2022-08-31
Anodic Electrocatalysis of Glycerol Oxidation for Hybrid Alkali/Acid Electrolytic Hydrogen Generation
Received date: 2022-06-01
Revised date: 2022-06-23
Accepted date: 2022-08-29
Online published: 2022-08-31
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。
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, 2023 , 29(2) : 2215005 . DOI: 10.13208/j.electrochem.2215005
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.
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [7] | Mallouk T E. Water electrolysis: Divide and conquer[J]. Nat. Chem., 2013, 5(5): 362-363. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [22] | Dodekatos G, Schünemann S, Tüysüz H. Recent advances in thermo-, photo-, and electrocatalytic glycerol oxidation[J]. ACS Catal., 2018, 8(7): 6301-6333. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
| [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. |
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