AI Chat Paper
Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
Search articles, authors, keywords, DOl and etc.
{{expandStatus?'Exit ':''}}Advanced Search
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] orCB [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 welldefined 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.
Nitopi S, Bertheussen E, Scott S B, Liu X Y, Engstfeld A K, Horch S, Seger B, Stephens I EL, 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.
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.
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.
Wu Z P, Lu X F, Zang S Q, Lou X W. Non-noble-metalbased electrocatalysts toward the oxygen evolution reaction [J]. Adv. Funct. Mater., 2020, 30(15): 1910274.
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.
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.
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.
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 (CNx) in acidic media[J]. Appl. Catal., B, 2018, 220: 88–97.
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.
Zhuang Z H, Chen W. Application of atomically precise metal nanoclusters in electrocatalysis[J]. J. Electrochem., 2021, 27(2): 125–143.
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.
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.
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.
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.
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.
Lagona J, Mukhopadhyay P, Chakrabarti S, Isaacs L. The cucurbit[n]uril family[J]. Angew. Chem. Int. Ed., 2005, 44(31): 4844–4870.
Brehrend R, Meyer E, Rusche F I. Ueber condensation-sproducte aus glycoluril und formaldehyd[J]. Eur. J. Org. Chem., 1905, 339(1): 1–37.
Freeman W A, Mock W L, Shih N Y. Cucurbituril[J]. J. Am. Chem. Soc., 1981, 103(24): 7367–7368.
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.
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.
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.
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.
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.
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.
Cao M N, Wu D S, Su W P, Cao R. Palladium nanocrystals stabilized by cucurbit[6]uril as efficient heterogeneous catalyst for direct ceh functionalization of polyfluoroarenes [J]. J. Catal., 2015, 321: 62–69.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Xie J, Peng H J, Huang J Q, Xu W T, Chen X, Zhang Q. A supramolecular capsule for reversible polysulfide stor-age/delivery in lithium-sulfur batteries[J]. Angew. Chem. Int. Ed., 2017, 56(51): 16223–16227.
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.
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.
Peng Q L, Chen J F, Ji H X, Morita A, Ye S. Origin of the overpotential for the oxygen evolution reaction on a welldefined graphene electrode probed by in situ sum frequency generation vibrational spectroscopy[J]. J. Am. Chem. Soc., 2018, 140(46): 15568–15571.
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.
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.
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.
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.
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.
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.
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.
This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-nc/4.0/).
京公网安备11010802044758号