瓜环基金属纳米催化剂的电化学研究进展

doi:10.13208/j.electrochem.2215008

摘要/Abstract

摘要：

金属纳米材料在电催化应用中展示出良好的性能，但是它们依旧面临着稳定性差和调控策略有限的问题。引入第二组分是一种有效的策略，能够很好的改善其催化活性与稳定性。在这篇综述中，我们概述了结合金属纳米材料和瓜环（CB[n]）用于电催化应用。瓜环是一系列的具有刚性结构、高稳定性、与金属配位的官能团的大环，它们适合稳定金属纳米材料并对其进行调控。本文讨论按照瓜环的功能分类，包含瓜环作为保护剂、瓜环基的超分子自组装体以及瓜环作为前驱体制备氮掺杂多孔碳。多种金属纳米催化剂，包括金属纳米颗粒（Pt，Ir，Pd，Ru，Au）、金属单原子（Fe，Co，Ni）以及过渡金属碳化物（TMCs）成功与瓜环或瓜环衍生的碳材料复合，这些复合材料在许多电催化反应中展示出优异的性能和稳定性，反应包括了氧还原反应（ORR）、析氧反应（OER）、析氢反应（HER）、二氧化碳还原反应（CO₂RR）、甲烷氧化反应（MOR）、乙醇氧化反应（EOR）。其中，一些金属-瓜环复合物可进一步作为双功能催化剂用于全水解和燃料电池中。瓜环基的纳米催化剂具有媲美商用催化剂的性能，其稳定性甚至可优于商用催化剂。实验分析以及密度泛函理论（DFT）计算均证明，该提升得益于瓜环和金属纳米晶之间的相互作用以及瓜环自身的稳定性。最后，我们讨论了瓜环基电催化剂的挑战与机遇。本综述提供了通过瓜环构筑具有优异性能的金属纳米材料，并期待该策略将有助于开发高效催化剂并用于更多的电化学应用中。

关键词: 电催化, 燃料电池, 电解水, 瓜环, 金属纳米材料

Abstract:

Metal nanomaterials have exhibited excellent performance in electrocatalytic applications, but they still face the problems of poor stability and limited regulation strategies. It is an efficient strategy for greatly enhanced catalytic activity and stability by introducing a second component. In this review, we provide the sketch for the combination of metal nanomaterials and cucurbit[n]urils (CB[n]s) in electrocatalytic applications. CB[n]s are a series of macrocycles with rigid structure, high stability, and function groups for coordinating with metal sites, which make them promising to stabilize and modulate the metal nanomaterials for ideal performance. The discussion classifies the roles of CB[n]s, involving CB[n]s as protecting agents, CB[n]-based supramolecular self-assemblies and CB[n]s as the precursor for the preparation of N-doped holy carbon matrix. Various metal nanocatalysts including metal (Pt, Ir, Pd, Ru, Au) nanoparticles, metal (Fe, Co, Ni) single-atoms, and transition metal carbides (TMCs) have been integrated with CB[n] or CB[n]-derived carbon matrix. These nanomaterials show superior activity and stability in multiple electrocatalytic reactions, including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO₂RR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR). Furthermore, a few metal-CB[n] composites can become bifunctional catalysts applied in the overall water splitting and fuel cell. It is surprising that the activity of CB[n]-based nanocatalysts is comparable with that of commercial catalyst, and the stability is even better. The experimental analysis together with the density functional theory (DFT) calculations verifies that the improvement can be attributed to the interaction between the metal nanocrystal and CB[n]s as well as the characteristic stability of CB[n]s. Finally, we talk about the challenges and opportunities for the cucurbit[n]uril-based electrocatalysis. This review provides an impressive strategy to obtain well-defined metal nanomaterials constructed with CB[n]s with enhanced performance, and expects that such a strategy will develop more efficient catalysts for a broader range of electro-applications.

Key words: Electrocatalysis, Fuel cells, Water splitting, Cucurbit[n]uril, Metal nanomaterials

韦宗楠, 曹敏纳, 曹荣. 瓜环基金属纳米催化剂的电化学研究进展[J]. 电化学（中英文）, 2023, 29(1): 2215008.

Zong-Nan Wei, Min-Na Cao, Rong Cao. Research Progress in Cucurbit[n]uril-Based Metal Nanomaterials for Electrocatalytic Applications[J]. Journal of Electrochemistry, 2023, 29(1): 2215008.

图/表 17

参考文献 49

[1]	Nitopi S, Bertheussen E, Scott S B, Liu X Y, Engstfeld A K, Horch S, Seger B, Stephens I E L, Chan K, Hahn C, Norskov J K, Jaramillo T F, Chorkendorff I. Progress and perspectives of electrochemical CO₂ reduction on copper in aqueous electrolyte[J]. Chem. Rev., 2019, 119(12): 7610-7672. doi: 10.1021/acs.chemrev.8b00705 URL
[2]	Jiang X, Nie X W, Guo X W, Song C S, Chen J G G. Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis[J]. Chem. Rev., 2020, 120(15): 7984-8034. doi: 10.1021/acs.chemrev.9b00723 pmid: 32049507
[3]	Zheng Y, Jiao Y, Vasileff A, Qiao S Z. The hydrogen evolution reaction in alkaline solution: From theory, single crystal models, to practical electrocatalysts[J]. Angew. Chem. Int. Ed., 2018, 57(26): 7568-7579. doi: 10.1002/anie.201710556 pmid: 29194903
[4]	Wu Z P, Lu X F, Zang S Q, Lou X W. Non‐noble‐metal‐based electrocatalysts toward the oxygen evolution reaction[J]. Adv. Funct. Mater., 2020, 30(15): 1910274. doi: 10.1002/adfm.v30.15 URL
[5]	Feng Y C, Wang X, Wang Y Q, Yan H J, Wang D. In situ characterization of electrode structure and catalytic processes in the electrocatalytic oxygen reduction reaction[J]. J. Electrochem., 2022, 28(3): 112-124.
[6]	Tomboc G M, Choi S, Kwon T, Hwang Y J, Lee K Y. Potential Link between Cu surface and selective CO₂ electroreduction: Perspective on future electrocatalyst designs[J]. Adv. Mater., 2020, 32(17): 1908398. doi: 10.1002/adma.v32.17 URL
[7]	Yao Q, Huang B L, Zhang N, Sun M Z, Shao Q, Huang X Q. Channel-rich RuCu nanosheets for pH-universal overall water splitting electrocatalysis[J]. Angew. Chem. Int. Ed., 2019, 58(39): 13983-13988. doi: 10.1002/anie.201908092 pmid: 31342633
[8]	Mamtani K, Jain D, Dogu D, Gustin V, Gunduz S, Co A C, Ozkan U S. Insights into oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) active sites for nitrogen-doped carbon nanostructures (CN_x) in acidic media[J]. Appl. Catal. B, 2018, 220: 88-97. doi: 10.1016/j.apcatb.2017.07.086 URL
[9]	Liu M L, Zhao Z P, Duan X F, Huang Y. Nanoscale structure design for high-performance Pt-based ORR catalysts[J]. Adv. Mater., 2019, 31(6): 1802234. doi: 10.1002/adma.v31.6 URL
[10]	Zhuang Z H, Chen W. Application of atomically precise metal nanoclusters in electrocatalysis[J]. J. Electrochem., 2021, 27(2): 125-143.
[11]	Loiudice A, Lobaccaro P, Kamali E A, Thao T, Huang B H, Ager J W, Buonsanti R. Tailoring copper nanocrystals towards C₂ products in electrochemical CO₂ reduction[J]. Angew. Chem. Int. Ed., 2016, 55(19): 5789-5792. doi: 10.1002/anie.201601582 pmid: 27059162
[12]	Huang J F, Hormann N, Oveisi E, Loiudice A, Gregorio G L, Andreussi O, Marzari N, Buonsanti R. Potential-induced nanoclustering of metallic catalysts during electrochemical CO₂ reduction[J]. Nat. Commun., 2018, 9: 3117 doi: 10.1038/s41467-018-05544-3
[13]	Qiu J C, Nguyen Q N, Lyu Z H, Wang Q X, Xia Y N. Bimetallic Janus nanocrystals: Syntheses and applications[J]. Adv. Mater., 2022, 34(1): 2102591. doi: 10.1002/adma.v34.1 URL
[14]	Mahmood J, Li F, Jung S M, Okyay M S, Ahmad I, Kim S J, Park N, Jeong H Y, Baek J B. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction[J]. Nat. Nanotechnol., 2017, 12(5): 441-446. doi: 10.1038/nnano.2016.304 pmid: 28192390
[15]	Wang H M, Chen Z N, Wu D S, Cao M N, Sun F F, Zhang H, You H H, Zhuang W, Cao R. Significantly enhanced overall water splitting performance by partial oxidation of Ir through Au modification in core-shell alloy structure[J]. J. Am. Chem. Soc., 2021, 143(12): 4639-4645. doi: 10.1021/jacs.0c12740 pmid: 33656891
[16]	Lagona J, Mukhopadhyay P, Chakrabarti S, Isaacs L. The cucurbit[n]uril family[J]. Angew. Chem. Int. Ed., 2005, 44(31): 4844-4870. doi: 10.1002/(ISSN)1521-3773 URL
[17]	Brehrend R, Meyer E, Rusche F. I. ueber condensationsproducte aus glycoluril und formaldehyd[J]. Eur. J. Org. Chem., 1905, 339(1): 1-37.
[18]	Freeman W A, Mock W L, Shih N Y. Cucurbituril[J]. J. Am. Chem. Soc., 1981, 103(24): 7367-7368. doi: 10.1021/ja00414a070 URL
[19]	Kim S Y, Jung I S, Lee E, Kim J, Sakamoto S, Yamaguchi K. Kim K. Macrocycles within macrocycles: Cyclen, cyclam, and their transition metal complexes encapsulated in cucurbit[8]uril[J]. Angew. Chem. Int. Ed., 2001, 40(11): 2119-2121. doi: 10.1002/(ISSN)1521-3773 URL
[20]	Zhao J Z, Kim H J, Oh J, Kim S Y, Lee J W, Sakamoto S, Yamaguchi K, Kim K. Cucurbit[n]uril derivatives soluble in water and organic solvents[J]. Angew. Chem. Int. Ed., 2001, 40(22): 4233-4235. doi: 10.1002/1521-3773(20011119)40:22<4233::AID-ANIE4233>3.0.CO;2-D pmid: 29712114
[21]	Lee J W, Samal S, Selvapalam N, Kim H J, Kim K. Cucurbituril homologues and derivatives: New opportunities in supramolecular chemistry[J]. Acc. Chem. Res., 2003, 36(8): 621-630. doi: 10.1021/ar020254k URL
[22]	Lee T C, Scherman O A. Formation of dynamic aggregates in water by cucurbit[5]uril capped with gold nanoparticles[J]. Chem. Commun., 2010, 46(14): 2438-2440. doi: 10.1039/b925051d URL
[23]	de la Rica R, Velders A H. Biomimetic crystallization of Ag₂S nanoclusters in nanopore assemblies[J]. J. Am. Chem. Soc., 2011, 133(9): 2875-2877. doi: 10.1021/ja110272g pmid: 21319820
[24]	Cao M N, Lin J X, Yang H X, Cao R. Facile synthesis of palladium nanoparticles with high chemical activity using cucurbit[6]uril as protecting agent[J]. Chem. Commun., 2010, 46(28): 5088-5090. doi: 10.1039/c0cc00541j URL
[25]	Cao M N, Wu D S, Su W P, Cao R. Palladium nanocrystals stabilized by cucurbit[6]uril as efficient heterogeneous catalyst for direct C-H functionalization of polyfluoroarenes[J]. J Catal., 2015, 321: 62-69. doi: 10.1016/j.jcat.2014.10.013 URL
[26]	Li H F, Lu J, Lin J X, Huang Y B, Cao M N, Cao R. Crystalline hybrid solid materials of palladium and decamethylcucurbit[5]uril as recoverable precatalysts for heck cross-coupling reactions[J]. Chem. Eur. J., 2013, 19(46): 15661-15668. doi: 10.1002/chem.v19.46 URL
[27]	Zhao F, Wen B, Niu W H, Chen Z, Yan C, Selloni A, Tully C G, Yang X F, Koel B E. Increasing iridium oxide activity for the oxygen evolution reaction with hafnium modification[J]. J. Am. Chem. Soc., 2021, 143(38): 15616-15623. doi: 10.1021/jacs.1c03473 pmid: 34469132
[28]	Yin J, Jin J, Lu M, Huang B L, Zhang H, Peng Y, Xi P X, Yan C H. Iridium single atoms coupling with oxygen vacancies boosts oxygen evolution reaction in acid media[J]. J. Am. Chem. Soc., 2020, 142(43): 18378-18386. doi: 10.1021/jacs.0c05050 URL
[29]	You H H, Wu D S, Chen Z N, Sun F F, Zhang H, Chen Z H, Cao M N, Zhuang W, Cao R. Highly active and stable water splitting in acidic media using a bifunctional iridium/cucurbit[6]uril catalyst[J]. ACS Energy Lett., 2019, 4(6): 1301-1307. doi: 10.1021/acsenergylett.9b00553 URL
[30]	Cao M N, Wu D S, Gao S Y, Cao R. Platinum nanoparticles stabilized by cucurbit[6]uril with enhanced catalytic activity and excellent poisoning tolerance for methanol electrooxidation[J]. Chem. Eur. J., 2012, 18(41): 12978-12985. doi: 10.1002/chem.201201817 URL
[31]	Wu D S, Cao M N, Cao R. Replacing PVP by macrocycle cucurbit[6]uril to cap sub-5 nm Pd nanocubes as highly active and durable catalyst for ethanol electrooxidation[J]. Nano Res., 2019, 12(10): 2628-2633. doi: 10.1007/s12274-019-2499-0
[32]	Zhang S Y, Cao M N, Cao R. Multipod Pd-cucurbit[6]uril as an efficient bifunctional electrocatalyst for ethanol oxidation and oxygen reduction reactions[J]. ACS Sustain. Chem. Eng., 2020, 8(24): 9217-9225. doi: 10.1021/acssuschemeng.0c03355 URL
[33]	Gong Z W, Wu D S, Cao M N, Zhao C, Cao R. Ultrafine Ru nanoclusters anchored on cucurbit[6]uril/rGO for efficient hydrogen evolution in a broad pH range[J]. Chem. Commun., 2020, 56(65): 9392-9395. doi: 10.1039/D0CC03652H URL
[34]	Chen R R, Cao M N, Yang W G, Wang H M, Zhang S Y, Li H F, Cao R. Ultra-small Pd nanoparticles derived from a supramolecular assembly for enhanced electrochemical reduction of CO₂ to CO[J]. Chem. Commun., 2019, 55(66): 9805-9808. doi: 10.1039/C9CC02393C URL
[35]	Song X M, Cao M N, Chen R R, Wang H M, Li H F, Cao R. Enhanced selectivity and stability towards CO₂ reduction of sub-5 nm Au NPs derived from supramolecular assembly[J]. Chem. Commun., 2021, 57(20): 2491-2494. doi: 10.1039/D0CC08353D URL
[36]	Chen R R, Cao M N, Wang J Y, Li H F, Cao R. Decamethylcucurbit[5]uril based supramolecular assemblies as efficient electrocatalysts for the oxygen reduction reaction[J]. Chem. Commun., 2019, 55(78): 11687-11690. doi: 10.1039/C9CC05899K URL
[37]	Khaligh A, Sheidaei Y, Tuncel D. Covalent organic framework constructed by clicking azido porphyrin with perpropargyloxy-cucurbit[6]uril for electrocatalytic hydrogen generation from water splitting[J]. ACS Appl. Energy Mater., 2021, 4(4): 3535-3543. doi: 10.1021/acsaem.0c03265 URL
[38]	Zhang C C, Liu X L, Liu Y P, Liu Y. Two-dimensional supramolecular nanoarchitectures of polypseudorotaxanes based on cucurbit[8]uril for highly efficient electrochemical nitrogen reduction[J]. Chem. Mater., 2020, 32(19): 8724-8732. doi: 10.1021/acs.chemmater.0c03425 URL
[39]	Xie J, Peng H J, Huang J Q, Xu W T, Chen X, Zhang Q. A supramolecular capsule for reversible polysulfide storage/delivery in lithium-sulfur batteries[J]. Angew. Chem. Int. Ed., 2017, 56(51): 16223-16227. doi: 10.1002/anie.201710025 pmid: 29112779
[40]	Xie J, Li B Q, Song Y W, Peng H J, Zhang Q. A supramolecular electrolyte for lithium-metal batteries[J]. Batteries & Supercaps, 2020, 3(1): 47-51.
[41]	Wang J, Ciucci F. In-situ synthesis of bimetallic phosphide with carbon tubes as an active electrocatalyst for oxygen evolution reaction[J]. Appl. Catal. B, 2019, 254: 292-299. doi: 10.1016/j.apcatb.2019.05.009 URL
[42]	Peng Q L, Chen J F, Ji H X, Morita A, Ye S. Origin of the overpotential for the oxygen evolution reaction on a well-defined graphene electrode probed by in situ sum frequency generation vibrational spectroscopy[J]. J. Am. Chem. Soc., 2018, 140(46): 15568-15571. doi: 10.1021/jacs.8b08285 URL
[43]	Sun H M, Tian C Y, Fan G L, Qi J N, Liu Z T, Yan Z H, Cheng F Y, Chen J, Li C P, Du M. Boosting activity on Co₄N porous nanosheet by coupling CeO₂ for efficient electrochemical overall water splitting at high current densities[J]. Adv. Funct. Mater., 2020, 30(32): 1910596. doi: 10.1002/adfm.v30.32 URL
[44]	Zhang X, Xu H M, Li X X, Li Y Y, Yang T B, Liang Y Y. Facile synthesis of nickel-iron/nanocarbon hybrids as advanced electrocatalysts for efficient water splitting[J]. ACS Catal., 2016, 6(2): 580-588. doi: 10.1021/acscatal.5b02291 URL
[45]	Wu D S, Cao M N, You H H, Zhao C, Cao R. N-doped holey carbon materials derived from a metal-free macrocycle cucurbit[6]uril assembly as an efficient electrocatalyst for the oxygen reduction reaction[J]. Chem. Commun., 2019, 55(92): 13832-13835. doi: 10.1039/C9CC06939A URL
[46]	Xie J, Li B Q, Peng H J, Song Y W, Li J X, Zhang Z W, Zhang Q. From supramolecular species to self-templated porous carbon and metal-doped carbon for oxygen reduction reaction catalysts[J]. Angew. Chem. Int. Ed., 2019, 58(15): 4963-4967. doi: 10.1002/anie.201814605 pmid: 30667570
[47]	Zhang S Y, Yang W G, Liang Y L, Yang X, Cao M N, Cao R. Template-free synthesis of non-noble metal single-atom electrocatalyst with N-doped holey carbon matrix for highly efficient oxygen reduction reaction in zinc-air batteries[J]. Appl. Catal. B, 2021, 285: 119780. doi: 10.1016/j.apcatb.2020.119780 URL
[48]	Zhao H L, Yang S B, Yang W G, Zhao C, Cao M N, Cao R. Ultrasmall Mo₂C embedded in N‐doped holey carbon for high‐efficiency electrochemical oxygen reduction reaction[J]. ChemElectroChem, 2022, 9(10): e202200141.
[49]	Xiao X, Zhang H, Xiong Y, Liang F, Yang Y W. Iridium-doped N-rich mesoporous carbon electrocatalyst with synthetic macrocycles as carbon source for hydrogen evolution reaction[J]. Adv. Funct. Mater., 2021, 31(42): 2105562. doi: 10.1002/adfm.v31.42 URL