Application of Atomically Precise Metal Nanoclusters in Electrocatalysis

Authors

Zhi-Hua Zhuang, 1. State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, Jilin, China;2. University of Science and Technology of China, Hefei 230026, Anhui, China;
Wei Chen, 1. State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, Jilin, China;2. University of Science and Technology of China, Hefei 230026, Anhui, China;Follow

Corresponding Author

Wei Chen(chenw@sari.ac.cn)

Abstract

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.

Graphical Abstract

Keywords

metal nanocluster, electrocatalysis, fuel cells, water splitting reaction, CO2 reduction reaction

DOI Link

https://doi.org/10.13208/j.electrochem.201246

Publication Date

2021-04-28

Online Available Date

2021-03-12

Revised Date

2021-03-02

Received Date

2021-01-31

Recommended Citation

Zhi-Hua Zhuang, Wei Chen. Application of Atomically Precise Metal Nanoclusters in Electrocatalysis[J]. Journal of Electrochemistry, 2021 , 27(2): 125-143.
DOI: 10.13208/j.electrochem.201246
Available at: https://jelectrochem.xmu.edu.cn/journal/vol27/iss2/6

References

[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.
doi: 10.1039/c2cs15325d URL

[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.
doi: 10.1021/acs.chemrev.5b00703 URL

[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.
doi: 10.1016/j.bios.2014.10.034 URL

[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.
doi: 10.1126/science.1159639 URL

[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.
doi: 10.1021/acssuschemeng.8b06637 URL

[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.
doi: 10.1021/cs300252g URL

[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.
doi: 10.1021/ja0782448 URL

[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.
doi: 10.1021/ja907627f URL

[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.
doi: 10.1038/nchem.288 URL

[11] Reetz M T, Helbig W. Size-selective synjournal of nanostructured transition metal clusters[J]. J. Am. Chem. Soc., 1994,116(16):7401-7402.
doi: 10.1021/ja00095a051 URL

[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.
doi: 10.1021/ja105495n URL

[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.
doi: 10.1021/nn401971g URL

[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.
doi: 10.1002/anie.200907120 URL

[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.
pmid: 16190687

[16] Jupally V R, Dass A. Synjournal of Au₁₃₀(SR)₅₀ and Au₁₃₀-x Ag_x(SR)₅₀ nanomolecules through core size conversion of larger metal clusters[J]. PCCP, 2014,16(22):10473-10479.
doi: 10.1039/C3CP54343A URL

[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.
doi: 10.1021/ac4023764 URL

[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.
doi: 10.1126/science.1134569 URL

[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.
doi: 10.1021/nn302984x URL

[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.
doi: 10.1016/j.jpowsour.2011.09.033 URL

[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.
doi: 10.1021/ja109303z URL

[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.
doi: 10.1002/celc.201600053 URL

[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 [Ag_xAu₂₅-_x(SC₆H₁₁)₁₈]- nanoclusters, cryogenic optical, electronic and electrocatalytic properties[J]. Nanoscale, 2017,9(48):19183-19190.
doi: 10.1039/C7NR05871C URL

[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.
doi: 10.1039/c3ta12067h URL

[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.
doi: 10.1016/j.electacta.2020.137608 URL

[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.
doi: 10.1021/acs.chemmater.9b05244 URL

[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.
doi: 10.1021/acscatal.9b03506 URL

[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.
doi: 10.1021/nn400772s URL

[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.
doi: 10.1039/C6NR00709K URL

[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.
doi: 10.1016/j.jpowsour.2012.12.009 URL

[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.
doi: 10.1039/c5nr01575h pmid: 26155948

[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.
doi: 10.1016/j.jcis.2018.12.015 URL

[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.
doi: 10.1016/j.nanoen.2018.05.052 URL

[34] Yeager E. Electrocatalysts for O₂ reduction[J]. Electrochim. Acta, 1984,29(11):1527-1537.
doi: 10.1016/0013-4686(84)85006-9 URL

[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.
doi: 10.1021/ja405922m URL

[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.
doi: 10.1002/(ISSN)1521-3773 URL

[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.
doi: 10.1039/C4CC01841A URL

[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.
doi: 10.1002/adfm.v28.43 URL

[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.
doi: 10.1021/jacs.6b11218 URL

[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.
doi: 10.1039/C7CC04787H URL

[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.
doi: 10.1021/acsaem.8b01783 URL

[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.
doi: 10.1039/C6CS00328A URL

[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.
doi: 10.1021/jacs.6b12529 URL

[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.
doi: 10.1021/acs.chemrev.5b00197 URL

[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.
doi: 10.1021/ja303259q URL

[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 Au₂₅^q nanoclusters (q = 1, 0, +1)[J]. Chem. Sci., 2014,5(8):3151-3157.
doi: 10.1039/c4sc00997e URL

[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.
doi: 10.1021/acscatal.8b00365 URL