原子数精确的金属纳米团簇在电催化领域的应用研究进展
收稿日期: 2021-01-31
修回日期: 2021-03-02
网络出版日期: 2021-03-12
基金资助
国家自然科学基金项目(21633008);国家自然科学基金项目(21773224);科技部重点研发计划(2020YFB1506001)
Application of Atomically Precise Metal Nanoclusters in Electrocatalysis
Received date: 2021-01-31
Revised date: 2021-03-02
Online published: 2021-03-12
金属纳米团簇（M NCs）是由几个到数百个金属原子组成,其尺寸一般小于2 nm。金属纳米团簇在许多催化反应中表现出高的催化活性和选择性,这与金属纳米团簇具有高的比表面积、较多暴露的活性原子,以及与金属纳米粒子（M NPs）不同的电子结构有关。金属纳米团簇确定的组成和结构使其成为一种新型模型催化剂,对纳米团簇的催化性能研究有利于人们深入理解催化剂结构-性质之间的关系,更利于催化剂的理性设计与发展。结合近几年国内外和本课题组在金属纳米团簇电催化领域的研究进展和现状,本文对该领域的代表性工作进行了简要综述,并对其未来在电催化领域的应用前景和需要解决的关键问题进行了展望。
庄志华 , 陈卫 . 原子数精确的金属纳米团簇在电催化领域的应用研究进展[J]. 电化学, 2021 , 27(2) : 125 -143 . DOI: 10.13208/j.electrochem.201246
Metal nanoclusters (M NCs) consist of only several to a few hundred of metal atoms and possess core sizes less than 2 nm. Owing to the quantum size effect, the electronic states of M NCs evolve to discrete levels similar to the molecule energy gaps, other than a continuous density of states to produce plasmon characteristic of bulk metal nanoparticles (M NPs). In comparison with the conventional M NPs, M NCs exhibit dramatically unique electronic and optical properties, such as molecule-like energy gaps, strong photoluminescence and high catalytic properties, which make them promising for potential application in numerous fields, such as catalysis, chemical sensors, electronics, biological labeling and biomedicine. As a new type of highly efficient catalysts, MNCs have shown high catalytic activity and unique selectivity in many catalytic reactions, which are related to their ultrasmall size with relatively high surface area-to-volume ratio, high density of exposed active atoms, and the unique electronic structure different from that of bulk M NPs. For example, the M NCs showed good performances in many catalytic reactions, such as CO oxidation, propylene epoxidation, electrocatalytic water oxidation, propane dehydrogenation, acetylene cyclotrimerization and hydrogenation and polymerization reactions. M NCs can be used as model catalysts for theoretical simulation of the reaction pathway due to the precise compositions, atomically precise and tunable structures, which is helpful to study the intrinsic relationship between structure and property of nanostructure, and to rational design and fabricate advanced catalysts. In this review article, based on the present status of this field, we highlight the development of metal nanoclusters in recent years with focusing mainly on their application in electrocatalysis, including for fuel cell anode and cathode reactions, water splitting reaction and CO2 reduction. Finally, we give a brief outlook on the application of metal nanoclusters in electrocatalysis and the possible challenges.
| [1] | Lu Y Z, Chen W. Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries[J]. Chem. Soc. Rev., 2012,41(9):3594-3623. |
| [2] | Jin R C, Zeng C J, Zhou M, Chen Y X. Atomically precise colloidal metal nanoclusters and nanoparticles: fundamentals and opportunities[J]. Chem. Rev., 2016,116(18):10346-10413. |
| [3] | Ding C Q, Tian Y. Gold nanocluster-based fluorescence biosensor for targeted imaging in cancer cells and ratiometric determination of intracellular pH[J]. Biosens. Bioelectron., 2015,65:183-190. |
| [4] | Herzing A A, Kiely C J, Carley A F, Landon P, Hutchings G J. Identification of active gold nanoclusters on iron oxide supports for CO oxidation[J]. Science, 2008,321(5894):1331-1335. |
| [5] | Zhuang Z H, Yang Q, Chen W. One-step rapid and facile synjournal of subnanometer-sized Pd6(C12H25S)11 clusters with ultra-high catalytic activity for 4-nitrophenol reduction[J]. ACS Sustainable Chem. Eng., 2019,7(3):2916-2923. |
| [6] | Xie S H, Tsunoyama H, Kurashige W, Negishi Y, Tsukuda T. Enhancement in aerobic alcohol oxidation catalysis of Au25 clusters by single Pd atom doping[J]. ACS Catal., 2012,2(7):1519-1523. |
| [7] | Brust M, Walker M, Bethell D, Schiffrin D, Whyman R. Synjournal of thiol-derivatized gold nanoparticles in a 2-phase liquid-liquid system[J]. Chem. Commun., 1994,7:801-802. |
| [8] | Zhu M Z, Lanni E, Garg N, Bier M E, Jin R C. Kinetically kontrolled, high-yield synjournal of Au25 clusters[J]. J. Am.Chem. Soc., 2008,130(4):1138-1139. |
| [9] | Wu Z K, Lanni E, Chen W, Bier M E, Ly D, Jin R. High yield, large scale synjournal of thiolate-protected Ag7 clusters[J]. J. Am. Chem. Soc., 2009,131(46):16672-16674. |
| [10] | Yamamoto K, Imaoka T, Chun W J, Enoki O, Katoh H, Takenaga M, Sonoi A. Size-specific catalytic activity of platinum clusters enhances oxygen reduction reactions[J]. Nat. Chem., 2009,1(5):397-402. |
| [11] | Reetz M T, Helbig W. Size-selective synjournal of nanostructured transition metal clusters[J]. J. Am. Chem. Soc., 1994,116(16):7401-7402. |
| [12] | Rao T U B, Nataraju B, Pradeep T. Ag9 quantum cluster through a solid-state route[J]. J. Am. Chem. Soc., 2010,132(46):16304-16307. |
| [13] | Zeng C J, Liu C Y, Pei Y, Jin R C. Thiol ligand-induced transformation of Au38(SC2H4Ph)24 to Au36(SPh-t-Bu)24[J]. ACS Nano, 2013,7(7):6138-6145. |
| [14] | Udaya Bhaskara Rao T, Pradeep T. Luminescent Ag7 and Ag8 clusters by interfacial synjournal[J]. Angew. Chem. Int. Ed., 2010,49(23):3925-3929. |
| [15] | Shichibu Y, Negishi Y, Tsukuda T, Teranishi T. Large-scale synjournal of thiolated Au25 clusters via ligand exchange reactions of phosphine-stabilized Au11 clusters[J]. J. Am. Chem. Soc., 2005,127(39):13464-13465. |
| [16] | Jupally V R, Dass A. Synjournal of Au130(SR)50 and Au130-x Agx(SR)50 nanomolecules through core size conversion of larger metal clusters[J]. PCCP, 2014,16(22):10473-10479. |
| [17] | Zhou T Y, Lin L P, Rong M C, Jiang Y Q, Chen X. Silver-gold alloy nanoclusters as a fluorescence-enhanced probe for aluminum ion sensing[J]. Anal. Chem., 2013,85(20):9839-9844. |
| [18] | Zhang J, Sasaki K, Sutter E, Adzic R R. Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters[J]. Science, 2007,315(5809):220-222. |
| [19] | Yin H J, Tang H J, Wang D, Gao Y, Tang Z Y. Facile synjournal of surfactant-free Au cluster/graphene hybrids for high-performance oxygen reduction reaction[J]. ACS Nano, 2012,6(9):8288-8297. |
| [20] | Lu Y Z, Chen W. Size effect of silver nanoclusters on their catalytic activity for oxygen electro-reduction[J]. J. Power Sources, 2012,197:107-110. |
| [21] | Wei W T, Lu Y Z, Chen W, Chen S W. One-pot synjournal, photoluminescence, and electrocatalytic properties of subnanometer-sized copper clusters[J]. J. Am. Chem. Soc., 2011,133(7):2060-2063. |
| [22] | Zhao S, Zhang H, House S D, Jin R, Yang J C, Jin R. Ultrasmall palladium nanoclusters as effective catalyst for xygen reduction reaction[J]. ChemElectroChem, 2016,3(8):1225-1229. |
| [23] | Jin R X, Zhao S, Liu C, Zhou M, Panapitiya G, Xing Y, Rosi N L, Lewis J P, Jin R C. Controlling Ag-doping in [AgxAu25-x(SC6H11)18]- nanoclusters, cryogenic optical, electronic and electrocatalytic properties[J]. Nanoscale, 2017,9(48):19183-19190. |
| [24] | Zhang R Z, Chen W. Non-precious Ir-V bimetallic nanoclusters assembled on reduced graphene nanosheets as catalysts for the oxygen reduction reaction[J]. J. Mater. Chem. A, 2013,1(37):11457-11464. |
| [25] | Zhuang Z H, Du C, Li P, Zhang Z W, Fang Z Y, Guo J H, Chen W. Pt21(C4O4SH5)21 clusters: atomically precise synjournal and enhanced electrocatalytic activity for hydrogen generation[J]. Electrochim. Acta, 2021,368:137608. |
| [26] | Yang T T, Tan T L, Saidi W A. High activity toward the hydrogen evolution reaction on the edges of MoS2-supported platinum nanoclusters using cluster expansion and electrochemical modeling[J]. Chem. Mater., 2020,32(3):1315-1321. |
| [27] | Li Y J, Pei W, He J T, Liu K, Qi W H, Gao X H, Zhou S, Xie H P, Yin K, Gao Y L, He J, Zhao J J, Hu J H, Chan T S, Li Z, Zhang G F, Liu M. Hybrids of PtRu nanoclusters and black phosphorus nanosheets for highly efficient alkaline hydrogen evolution reaction[J]. ACS Catal., 2019,9(12):10870-10875. |
| [28] | Kwon G, Ferguson G A, Heard C J, Tyo E C, Yin C, Debartolo J, Seifert S, Winans R E, Kropf A J, Greeley J, Johnston R L, Curtiss L A, Pellin M J, Vajda S. Size-dependent subnanometer Pd cluster (Pd4, Pd6, and Pd17) water oxidation electrocatalysis[J]. ACS Nano, 2013,7(7):5808-5817. |
| [29] | Joya K S, Sinatra L, Abdulhalim L G, Joshi C P, Hedhili M N, Bakr O M, Hussain I. Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation[J]. Nanoscale, 2016,8(18):9695-9703. |
| [30] | Bahrami H, Faghri A. Review and advances of direct methanol fuel cells: Part II: Modeling and numerical simulation[J]. J. Power Sources, 2013,230:303-320. |
| [31] | Mahata A, Choudhuri I, Pathak B. A cuboctahedral platinum (Pt79) nanocluster enclosed by well defined facets favours di-sigma adsorption and improves the reaction kinetics for methanol fuel cells[J]. Nanoscale, 2015,7(32):13438-13451. |
| [32] | Zhuang Z H, Chen W. Ultra-low loading of Pd5 nanoclusters on carbon nanotubes as bifunctional electrocatalysts for the oxygen reduction reaction and the ethanol oxidation reaction[J]. J. Colloid Interface Sci., 2019,538:699-708. |
| [33] | Lu Y Z, Zhang C M, Li X K, Frojd A R, Xing W, Clayborne A Z, Chen W. Significantly enhanced electrocatalytic activity of Au25 clusters by single platinum atom doping[J]. Nano Energy, 2018,50:316-322. |
| [34] | Yeager E. Electrocatalysts for O2 reduction[J]. Electrochim. Acta, 1984,29(11):1527-1537. |
| [35] | Imaoka T, Kitazawa H, Chun W J, Omura S, Albrecht K, Yamamoto K. Magic number Pt13 and misshapen Pt12 clusters: Which one is the better catalyst?[J]. J. Am. Chem. Soc., 2013,135(35):13089-13095. |
| [36] | Imaoka T, Kitazawa H, Chun W J, Yamamoto K. Finding the most catalytically active platinum clusters with low atomicity[J]. Angew. Chem. Int. Ed., 2015,54(34):9809-9815. |
| [37] | Chen W, Chen S W. Oxygen electroreduction catalyzed by gold nanoclusters: strong core size effects[J]. Angew. Chem. Int. Ed., 2009,48(24):4386-4389. |
| [38] | Lu Y Z, Jiang Y Y, Gao X H, Chen W. Charge state-dependent catalytic activity of [Au25(SC12H25)18] nanoclusters for the two-electron reduction of dioxygen to hydrogen peroxide[J]. Chem. Commun., 2014,50(62):8464-8467. |
| [39] | Zhao G Q, Rui K, Dou S X, Sun W P. Heterostructures for electrochemical hydrogen evolution reaction: A review[J]. Adv. Funct. Mater., 2018,28(43):1803291. |
| [40] | Wang S T, Gao X H, Hang X X, Zhu X F, Han H T, Liao W P, Chen W. Ultrafine Pt nanoclusters confined in a calixarene-based {Ni24} coordination cage for high-efficient hydrogen evolution reaction[J]. J. Am. Chem. Soc., 2016,138(50):16236-16239. |
| [41] | Gao X H, Chen W. Highly stable and efficient Pd6(SR)12 cluster catalysts for the hydrogen and oxygen evolution reactions[J]. Chem. Commun., 2017,53(70):9733-9736. |
| [42] | Gao X H, Yu G T, Zheng L R, Zhang C M, Li H, Wang T, An P D, Liu M, Qiu X Q, Chen W. Strong electron coupling from the sub-nanometer Pd clusters confined in porous ceria nanorods for highly efficient electrochemical hydrogen eevolution reaction[J]. ACS Appl. Energy Mater., 2019,2(2):966-973. |
| [43] | Suen N T, Hung S F, Quan Q, Zhang N, Xu Y J, Chen H M. Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives[J]. Chem. Soc. Rev., 2017,46(2):337-365. |
| [44] | Zhao S, Jin R X, Abroshan H, Zeng C J, Zhang H, House S D, Gottlieb E, Kim H J, Yang J C, Jin R C. Gold nanoclusters promote electrocatalytic water oxidation at the nanocluster/CoSe2 interface[J]. J. Am. Chem. Soc., 2017,139(3):1077-1080. |
| [45] | Wang W H, Himeda Y, Muckerman J T, Manbeck G F, Fujita E. CO2 hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO2 reduction[J]. Chem. Rev., 2015,115(23):12936-12973. |
| [46] | Kauffman D R, Alfonso D, Matranga C, Qian H F, Jin R C. Experimental and computational investigation of Au25 clusters and CO2: A unique interaction and enhanced electrocatalytic activity[J]. J. Am. Chem. Soc., 2012,134(24):10237-10243. |
| [47] | Kauffman D R, Alfonso D, Matranga C, Ohodnicki P, Deng X Y, Siva R C, Zeng C J, Jin R C. Probing active site chemistry with differently charged Au25q nanoclusters (q = 1, 0, +1)[J]. Chem. Sci., 2014,5(8):3151-3157. |
| [48] | Zhao S, Austin N, Li M, Song Y B, House S D, Bernhard S, Yang J C, Mpourmpakis G, Jin R C. Influence of atomic-level morphology on catalysis: The case of sphere and rod-like gold nanoclusters for CO2 electroreduction[J]. ACS Catal., 2018,8(6):4996-5001. |
/
| 〈 |
|
〉 |
