氮掺杂碳纳米管上钴和钌位点之间的电子通信促进碱性析氢反应

doi:10.61558/2993-074X.3460

摘要/Abstract

摘要：

碱性电解水析氢反应作为获取绿色氢能源的重要途径具有广泛的研究意义和应用价值，但其缓慢的电极反应动力学及较高的过电位需要高效稳定的催化剂来加速反应过程。目前商用的铂（Pt）基催化剂因高昂的成本限制了其规模化应用。设计高效、低过电位的非 Pt 电催化剂仍然是一个重大挑战。钌（Ru）基催化剂因具有类 Pt 的活性氢结合能而受到广泛关注。本文以富勒醇和三聚氰胺为基体原料，与氯化钴和氯化钌在 150 °C 水热反应 24 小时，随后在氩气/氢气（5%）混合气氛下 600 °C热解处理，成功在氮掺杂碳纳米管（N-CNTs）上修饰了钴钌（CoRu）纳米合金，制备了一种新型高效的 Co，Ru 双金属电催化剂。得益于 Co 和 Ru 位点之间的电子通信，所得 CoRu@N-CNTs 具有优异的电催化析氢反应活性。在 1 mol·L ^-1 氢氧化钾水溶液中达到 10 mA·cm ^-2 的电流密度，所需过电位仅为 19 mV，塔菲尔斜率为 26.19 mV·dec^-1，优于基准 Pt/C 催化剂。本研究将为高效析氢电催化剂的设计与制造开辟一条新的道路，有力推动电解水制氢技术在能源存储与转化领域的应用推广，为我国“碳达峰与碳中和”战略目标的实施蓄势赋能。

关键词: 钴钌合金, 电催化剂, 水裂解, 析氢反应, 碳纳米管

Abstract:

Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction (HER) remains a significant challenge. Here, a novel and efficient cobalt (Co), ruthenium (Ru) bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes (CoRu@N-CNTs), was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis. Benefiting from the electronic communication between Co and Ru sites, the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity. To deliver a current density of 10 mA·cm^-2, it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^-1 in 1 mol·L^-1 potassium hydroxide (KOH) solution, outperforming the benchmark Pt/C catalyst. The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.

Key words: CoRu alloy, Electrocatalyst, Water splitting, Hydrogen evolution reaction, Carbon nanotubes

高梦婷, 卫莹, 霍雪萌, 朱文洁, 刘箐箐, 强晋源, 刘婉婉, 王颖, 李旭, 黄剑锋, 冯永强. 氮掺杂碳纳米管上钴和钌位点之间的电子通信促进碱性析氢反应[J]. 电化学（中英文）, 2024, 30(9): 2403081.

Meng-Ting Gao, Ying Wei, Xue-Meng Hu, Wenj-Jie Zhu, Qing-Qing Liu, Jin-Yuan Qiang, Wan-Wan Liu, Ying Wang, Xu Li, Jian-Feng Huang, Yong-Qiang Feng. Electronic Communication between Co and Ru Sites Decorated on Nitrogen-Doped Carbon Nanotubes Boosting the Alkaline Hydrogen Evolution Reaction[J]. Journal of Electrochemistry, 2024, 30(9): 2403081.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3460

https://electrochem.xmu.edu.cn/CN/Y2024/V30/I9/2403081

图/表 5

参考文献 50

[1]	Qiao M F, Wang Y, Wang Q, Hu G Z, Mamat X, Zhang S S, Wang S Y. Hierarchically ordered porous carbon with atomically dispersed FeN₄ for ultraefficient oxygen reduction reaction in proton-exchange membrane fuel cells[J]. Angew. Chem. Int. Ed., 2020, 59(7): 2688-2694.
[2]	Wang J H, Cui W, Liu Q, Xing Z C, Asiri A M, Sun X P. Recent progress in cobalt-based heterogeneous catalysts for electrochemical water splitting[J]. Adv. Mater., 2016, 28(2): 215-230.
[3]	Hodges A, Hoang A L, Tsekouras G, Wagner K, Lee C Y, Swiegers G F, Wallace G G. A high-performance capillary-fed electrolysis cell promises more cost-competitive renewable hydrogen[J]. Nat. Commun., 2022, 13(1): 1304. doi: 10.1038/s41467-022-28953-x pmid: 35292657
[4]	Chu C H, Huang D H, Gupta S, Weon S, Niu J F, Stavitski E, Muhich C, Kim J H. Neighboring Pd single atoms surpass isolated single atoms for selective hydrodehalogenation catalysis[J]. Nat. Commun., 2021, 12(1): 5179. doi: 10.1038/s41467-021-25526-2 pmid: 34462434
[5]	Kang J X, Qiu X Y, Hu Q, Zhong J, Gao X, Huang R, Wan C Z, Liu L M, Duan X F, Guo L. Valence oscillation and dynamic active sites in monolayer NiCo hydroxides for water oxidation[J]. Nat. Catal., 2021, 4(12): 1050-1058.
[6]	Gao T T, Li X Q, Chen X J, Zhou C X, Yue Q, Yuan H Y, Xiao D. Ultra-fast preparing carbon nanotube-supported trimetallic Ni, Ru, Fe heterostructures as robust bifunctional electrocatalysts for overall water splitting[J]. Chem. Eng. J., 2021, 424: 130416.
[7]	Wang T J, Jiang Y C, He J W, Li F M, Ding Y, Chen P, Chen Y. Porous palladium phosphide nanotubes for formic acid electrooxidation[J]. Carbon Energy, 2022, 4(3): 283-293.
[8]	Jiang W J, Tang T, Zhang Y, Hu J S. Synergistic modulation of non-precious-metal electrocatalysts for advanced water splitting[J]. Acc. Chem. Res., 2020, 53(6): 1111-1123.
[9]	Huang C, Ouyang T, Zou Y, Li N, Liu Z Q. Ultrathin NiCo₂Px nanosheets strongly coupled with CNTs as efficient and robust electrocatalysts for overall water splitting[J]. J. Mater. Chem. A, 2018, 6(17): 7420-7427.
[10]	Olabi A G, Abdelkareem M A. Renewable energy and climate change[J]. Renew. Sus. Energ. Rev., 2022, 158: 112111.
[11]	Wang X N, Zhao L M, Li X J, Liu Y, Wang Y S, Yao Q F, Xie J P, Xue Q Z, Yan Z F, Yuan X, Xing W. Atomic-precision Pt₆ nanoclusters for enhanced hydrogen electro-oxidation[J]. Nat. Commun., 2022, 13(1): 1596.
[12]	Zaman S, Huang L, Douka A I, Yang H, You B, Xia B Y. Oxygen reduction electrocatalysts toward practical fuel cells: Progress and perspectives[J]. Angew. Chem. Int. Ed., 2021, 60(33): 17832-17852. doi: 10.1002/anie.202016977 pmid: 33533165
[13]	Chen H, Zhang B, Liang X, Zou X X. Light alloying element-regulated noble metal catalysts for energy-related applications[J]. Chinese J. Catal., 2022, 43(3): 611-635.
[14]	Sun Y M, Xue Z Q, Liu Q L, Jia Y L, Li Y L, Liu K, Lin Y Y, Liu M, Li G Q, Su C Y. Modulating electronic structure of metal-organic frameworks by introducing atomically dispersed Ru for efficient hydrogen evolution[J]. Nat. Commun., 2021, 12(1): 1369. doi: 10.1038/s41467-021-21595-5 pmid: 33649349
[15]	Clay C, Haq S, Hodgson A. Intact and dissociative adsorption of water on Ru(0001)[J]. Chem. Phys. Lett., 2004, 388(1): 89-93.
[16]	Cao X J, Huo J J, Li L, Qu J P, Zhao Y F, Chen W H, Liu C T, Liu H, Wang G X. Recent advances in engineered Ru-based electrocatalysts for the hydrogen/oxygen conversion reactions[J]. Adv. Energy Mater., 2022, 12(41): 2202119.
[17]	Liu Z, Zeng L L, Yu J Y, Yang L J, Zhang J, Zhang X L, Han F, Zhao L L, Li X, Liu H, Zhou W J. Charge redistribution of Ru nanoclusters on Co₃O₄ porous nanowire via the oxygen regulation for enhanced hydrogen evolution reaction[J]. Nano Energy, 2021, 85: 105940.
[18]	Wang Y J, Luo W J, Li H J, Cheng C A W. Ultrafine Ru nanoclusters supported on N/S doped macroporous carbon spheres for efficient hydrogen evolution reaction[J]. Nanoscale Adv., 2021, 3(17): 5068-5074. doi: 10.1039/d1na00424g pmid: 36132347
[19]	Wu Y L, Li X, Wei Y S, Fu Z, Wei W, Wu X T, Zhu Q L, Xu Q. Ordered macroporous superstructure of nitrogen-doped nanoporous carbon implanted with ultrafine Ru nanoclusters for efficient pH-universal hydrogen evolution reaction[J]. Adv. Mater., 2021, 33(12): 2006965.
[20]	Zhang X L, Ma J, Yan R W, Cheng W X, Zheng J, Jin B K. Pt-Ru/polyaniline/carbon nanotube composites with three-layer tubular structure for efficient methanol oxidation[J]. J. Alloy. Compd, 2021, 867: 159017.
[21]	Zhai P L, Xia M Y, Wu Y Z, Zhang G H, Gao J F, Zhang B, Cao S Y, Zhang Y T, Li Z W, Fan Z Z, Wang C, Zhang X M, Miller J T, Sun L C, Hou J G. Engineering single-atomic ruthenium catalytic sites on defective nickel-iron layered double hydroxide for overall water splitting[J]. Nat. Commun., 2021, 12(1): 4587. doi: 10.1038/s41467-021-24828-9 pmid: 34321467
[22]	Han X, Li Y J, Wang X, Dong J T, Li H M, Yin S, Xia J X. Ru anchored on Co(OH)2 nanowire arrays as highly effective electrocatalyst for full water splitting[J]. Int. J. Hydrogen Energ., 2024, 51: 769-776.
[23]	Liu Z, Yang X D, Hu G Z, Feng L G. Ru nanoclusters coupled on Co/N-doped carbon nanotubes efficiently catalyzed the hydrogen evolution reaction[J]. ACS Sustain. Chem. Eng., 2020, 8(24): 9136-9144.
[24]	Shah K, Dai R Y, Mateen M, Hassan Z, Zhuang Z W, Liu C H, Israr M, Cheong W C, Hu B T, Tu R Y, Zhang C, Chen X, Peng Q, Chen C, Li Y D. Cobalt single atom incorporated in ruthenium oxide sphere: A robust bifunctional electrocatalyst for HER and OER[J]. Angew. Chem. Int. Ed., 2022, 61(4): e202114951.
[25]	Martínez-Séptimo A, Valenzuela M A, Del Angel P, González-Huerta G R. Irruox/TiO₂ a stable electrocatalyst for the oxygen evolution reaction in acidic media[J]. Int. J. Hydrogen Energ., 2021, 46(51): 25918-25928.
[26]	Li G K, Jang H, Liu S G, Li Z J, Kim M G, Qin Q, Liu X, Cho J. The synergistic Effect of Hf-O-Ru Bonds and oxygen vacancies in Ru/HfO₂ for enhanced hydrogen evolution[J]. Nat. Commun., 2022, 13(1): 1270.
[27]	Feng W H, Feng Y Q, Chen J S, Wang H, Hu Y Z, Luo T M, Yuan C K, Cao L Y, Feng L L, Huang J F. Interfacial electronic engineering of Ru/FeRu nanoparticles as efficient trifunctional electrocatalyst for overall water splitting and Zn-Air battery[J]. Chem. Eng. J., 2022, 437: 135456.
[28]	Lin S Y, Chen Y P, Cao Y, Zhang L, Feng J J, Wang A J. Aminouracil-assisted synthesis of CoFe decorated bougainvillea-like N-doped carbon nanoflowers for boosting Zn-Air battery and water electrolysis[J]. J. Power Sources, 2022, 521: 230926.
[29]	Song H Q, Wu M, Tang Z Y, Tse J S, Yang B, Lu S Y. Single atom ruthenium-doped CoP/CDs nanosheets via splicing of carbon-dots for robust hydrogen production[J]. Angew. Chem. Int. Ed., 2021, 60(13): 7234-7244. doi: 10.1002/anie.202017102 pmid: 33438321
[30]	Kumar A, Bui V Q, Lee J, Wang L, Jadhav A R, Liu X, Shao X, Liu Y, Yu J, Hwang Y, Bui H T D, Ajmal S, Kim M G, Kim S G, Park G S, Kawazoe Y, Lee H. Moving beyond bimetallic-alloy to single-atom dimer atomic-interface for all-pH hydrogen evolution[J]. Nat. Commun., 2021, 12(1): 6766. doi: 10.1038/s41467-021-27145-3 pmid: 34799571
[31]	Lu Z Y, Wang B F, Hu Y F, Liu W, Zhao Y F, Yang R O, Li Z P, Luo J, Chi B, Jiang Z, Li M S, Mu S C, Liao S J, Zhang J J, Sun X L. An isolated zinc-cobalt atomic pair for highly active and durable oxygen reduction[J]. Angew. Chem. Int. Ed., 2019, 58(9): 2622-2626. doi: 10.1002/anie.201810175 pmid: 30600864
[32]	Bai L, Hsu C S, Alexander D T L, Chen H M, Hu X. Double-atom catalysts as a molecular platform for heterogeneous oxygen evolution electrocatalysis[J]. Nat. Energy, 2021, 6(11): 1054-1066.
[33]	Liu D B, Zhao Y, Wu C Q, Xu W J, Xi S B, Chen M X, Yang L, Zhou Y Z, He Q, Li X Y, Ge B H, Song L, Jiang J, Yan Q Y. Triggering electronic coupling between neighboring hetero-diatomic metal sites promotes hydrogen evolution reaction kinetics[J]. Nano Energy, 2022, 98: 107296.
[34]	Li J Z, Hou C Z, Chen C, Ma W S, Li Q, Hu L W, Lv X W, Dang J. Collaborative interface optimization strategy guided ultrafine RuCo and Mxene heterostructure electrocatalysts for efficient overall water splitting[J]. ACS Nano, 2023, 17(11): 10947-10957.
[35]	Su K Y, Yang S, Yang A Z, Guo Y, Liu B, Zhu J W, Tang Y W, Qiu X Y. Customizing the anisotropic electronic states of Janus-distributive FeN₄ and NiN₄ dual-atom sites for reversible oxygen electrocatalysis[J]. Appl. Catal. B-Environ., 2023, 331: 122694.
[36]	Luo T M, Huang J F, Hu Y Z, Yuan C K, Chen J S, Cao L Y, Kajiyoshi K, Liu Y J, Zhao Y, Li Z J, Feng Y Q. Fullerene lattice-confined Ru nanoparticles and single atoms synergistically boost electrocatalytic hydrogen evolution reaction[J]. Adv. Funct. Mater., 2023, 33(12): 2213058.
[37]	Wei C, Rao R R, Peng J, Huang B, Stephens I E L, Risch M, Xu Z J, Shao-Horn Y. Recommended practices and benchmark activity for hydrogen and oxygen electrocatalysis in water splitting and fuel cells[J]. Adv. Mater., 2019, 31(31): 1806296.
[38]	Chen J, Huang J, Wang R, Feng W, Wang H, Luo T, Hu Y, Yuan C, Feng L, Cao L, Kajiyoshi K, He C, Liu Y, Li Z, Feng Y. Atomic ruthenium coordinated with chlorine and nitrogen as efficient and multifunctional electrocatalyst for overall water splitting and rechargeable zinc-air battery[J]. Chem. Eng. J., 2022, 441: 136078.
[39]	Feng Y Q, Li X, Liu Q Q, Zhu W J, Huo X M, Gao M T, Liu W W, Wang Y, Wei Y. Fullerene-derived nanocomposite as an efficient electrocatalyst for overall water splitting and Zn-air battery[J]. Mater. Chem. Front., 2023, 7(24): 6446-6462.
[40]	Chen J S, Huang J F, Zhao Y, Cao L Y, Kajiyoshi K, Liu Y J, Li Z J, Feng Y Q. Enhancing the electronic metal-support interaction of CoRu alloy and pyridinic N for electrocatalytic pH-universal hydrogen evolution reaction[J]. Chem. Eng. J., 2022, 450: 138026.
[41]	Duan S S, Han G S, Su Y H, Zhang X Y, Liu Y Y, Wu X L, Li B J. Magnetic Co@G-C₃N₄ core-shells on rGO sheets for momentum transfer with catalytic activity toward continuous-flow hydrogen generation[J]. Langmuir, 2016, 32(25): 6272-6281.
[42]	Zhang F F, Zhu Y L, Chen Y, Lu Y Z H, Lin Q, Zhang L, Tao S W, Zhang X W, Wang H T. RuCo alloy bimodal nanoparticles embedded in N-doped carbon: a superior pH-universal electrocatalyst outperforms benchmark Pt for the hydrogen evolution reaction[J]. J. Mater. Chem. A, 2020, 8(25): 12810-12820.
[43]	Zhang M L, Wang J L, Zhang Y Q, Ye L, Gong Y Q. Ultrafine CoRu alloy nanoparticles in situ embedded in Co₄N Porous nanosheets as high-efficient hydrogen evolution electrocatalysts[J]. Dalton Trans., 2021, 50(8): 2973-2980.
[44]	Chen J, Ha Y, Wang R R, Liu Y X, Xu H B, Shang B, Wu R B, Pan H G. Inner Co synergizing outer Ru supported on carbon nanotubes for efficient pH-universal hydrogen evolution catalysis[J]. Nano-Micro Lett., 2022, 14(1): 186. doi: 10.1007/s40820-022-00933-2 pmid: 36104459
[45]	Cao D, Wang J Y, Xu H X, Cheng D J. Construction of dual-site atomically dispersed electrocatalysts with Ru-C₅ single atoms and Ru-O₄ nanoclusters for accelerated alkali hydrogen evolution[J]. Small, 2021, 17(31): 2101163.
[46]	Tiwari J N, Harzandi A M, Ha M, Sultan S, Myung C W, Park H J, Kim D Y, Thangavel P, Singh A N, Sharma P, Chandrasekaran S S, Salehnia F, Jang J W, Shin H S, Lee Z, Kim K S. High-performance hydrogen evolution by Ru single atoms and nitrided-Ru nanoparticles implanted on N-Doped graphitic sheet[J]. Adv. Energy Mater., 2019, 9(26): 1900931.
[47]	Zhao D, Sun K A, Cheong W C, Zheng L R, Zhang C, Liu S J, Cao X, Wu K L, Pan Y, Zhuang Z W, Hu B T, Wang D S, Peng Q, Chen C, Li Y D. Synergistically interactive pyridinic-N-MoP sites: Identified active centers for enhanced hydrogen evolution in alkaline solution[J]. Angew. Chem. Int. Ed., 2020, 59(23): 8982-8990. doi: 10.1002/anie.201908760 pmid: 31515887
[48]	Yu W H, Huang H, Qin Y N, Zhang D, Zhang Y Y, Liu K, Zhang Y, Lai J P, Wang L. The synergistic effect of pyrrolic-N and pyridinic-N with Pt under strong metal-support interaction to achieve high-performance alkaline hydrogen evolution[J]. Adv. Energy Mater., 2022, 12(21): 2200110.
[49]	Chen Y W, Ding R, Li J, Liu J G. Highly active atomically dispersed platinum-based electrocatalyst for hydrogen evolution reaction achieved by defect anchoring strategy[J]. Appl. Catal. B-Environ., 2022, 301: 120830.
[50]	Su P P, Pei W, Wang X W, Ma Y F, Jiang Q K, Liang J, Zhou S, Zhao J J, Liu J, Lu G Q. Exceptional electrochemical HER performance with enhanced electron transfer between Ru nanoparticles and single atoms dispersed on a carbon substrate[J]. Angew. Chem. Int. Ed., 2021, 60(29): 16044-16050.