Fast Site-to-site Electron Transfer of High-entropy Alloy Nanocatalyst Driving Redox Electrocatalysis

Overview

Journal Nat Commun

Specialty Biology

Date 2020 Oct 29

PMID 33116124

Citations 38

Authors

Hongdong Li

Yi Han

Huan Zhao

Wenjing Qi

Dan Zhang

Yaodong Yu

Wenwen Cai

Shaoxiang Li

Jianping Lai

Bolong Huang

Lei Wang

Affiliations

Soon will be listed here.

Abstract

Designing electrocatalysts with high-performance for both reduction and oxidation reactions faces severe challenges. Here, the uniform and ultrasmall (~3.4 nm) high-entropy alloys (HEAs) PtNiFeCoCu nanoparticles are synthesized by a simple low-temperature oil phase strategy at atmospheric pressure. The PtNiFeCoCu/C catalyst exhibits excellent electrocatalytic performance for hydrogen evolution reaction (HER) and methanol oxidation reaction (MOR). The catalyst shows ultrasmall overpotential of 11 mV at the current density of 10 mA cm, excellent activity (10.96 A mg at -0.07 V vs. reversible hydrogen electrode) and stability in the alkaline medium. Furthermore, it is also the efficient catalyst (15.04 A mg) ever reported for MOR in alkaline solution. Periodic DFT calculations confirm the multi-active sites for both HER and MOR on the HEA surface as the key factor for both proton and intermediate transformation. Meanwhile, the construction of HEA surfaces supplies the fast site-to-site electron transfer for both reduction and oxidation processes.

Citing Articles

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References

Xiong L, Sun Z, Zhang X, Zhao L, Huang P, Chen X . Octahedral gold-silver nanoframes with rich crystalline defects for efficient methanol oxidation manifesting a CO-promoting effect. Nat Commun. 2019; 10(1):3782. PMC: 6706449. DOI: 10.1038/s41467-019-11766-w. View

Koo W, Millstone J, Weiss P, Kim I . The Design and Science of Polyelemental Nanoparticles. ACS Nano. 2020; 14(6):6407-6413. DOI: 10.1021/acsnano.0c03993. View

Seh Z, Kibsgaard J, Dickens C, Chorkendorff I, Norskov J, Jaramillo T . Combining theory and experiment in electrocatalysis: Insights into materials design. Science. 2017; 355(6321). DOI: 10.1126/science.aad4998. View

Xie P, Yao Y, Huang Z, Liu Z, Zhang J, Li T . Highly efficient decomposition of ammonia using high-entropy alloy catalysts. Nat Commun. 2019; 10(1):4011. PMC: 6728353. DOI: 10.1038/s41467-019-11848-9. View

Chen P, Liu X, Hedrick J, Xie Z, Wang S, Lin Q . Polyelemental nanoparticle libraries. Science. 2016; 352(6293):1565-9. DOI: 10.1126/science.aaf8402. View

Chen Y, Lai Z, Zhang X, Fan Z, He Q, Tan C . Phase engineering of nanomaterials. Nat Rev Chem. 2023; 4(5):243-256. DOI: 10.1038/s41570-020-0173-4. View

Jin H, Guo C, Liu X, Liu J, Vasileff A, Jiao Y . Emerging Two-Dimensional Nanomaterials for Electrocatalysis. Chem Rev. 2018; 118(13):6337-6408. DOI: 10.1021/acs.chemrev.7b00689. View

Yin H, Dou Y, Chen S, Zhu Z, Liu P, Zhao H . 2D Electrocatalysts for Converting Earth-Abundant Simple Molecules into Value-Added Commodity Chemicals: Recent Progress and Perspectives. Adv Mater. 2019; 32(18):e1904870. DOI: 10.1002/adma.201904870. View

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

10.

Tian X, Zhao X, Su Y, Wang L, Wang H, Dang D . Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science. 2019; 366(6467):850-856. DOI: 10.1126/science.aaw7493. View

11.

Huang W, Wang H, Zhou J, Wang J, Duchesne P, Muir D . Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum-nickel hydroxide-graphene. Nat Commun. 2015; 6:10035. PMC: 4674678. DOI: 10.1038/ncomms10035. View

12.

Lei Z, Liu X, Wu Y, Wang H, Jiang S, Wang S . Enhanced strength and ductility in a high-entropy alloy via ordered oxygen complexes. Nature. 2018; 563(7732):546-550. DOI: 10.1038/s41586-018-0685-y. View

13.

You B, Liu X, Hu G, Gul S, Yano J, Jiang D . Universal Surface Engineering of Transition Metals for Superior Electrocatalytic Hydrogen Evolution in Neutral Water. J Am Chem Soc. 2017; 139(35):12283-12290. DOI: 10.1021/jacs.7b06434. View

14.

Luo X, Liu C, Wang X, Shao Q, Pi Y, Zhu T . Spin Regulation on 2D Pd-Fe-Pt Nanomeshes Promotes Fuel Electrooxidations. Nano Lett. 2020; 20(3):1967-1973. DOI: 10.1021/acs.nanolett.9b05250. View

15.

Lai J, Guo S . Design of Ultrathin Pt-Based Multimetallic Nanostructures for Efficient Oxygen Reduction Electrocatalysis. Small. 2017; 13(48). DOI: 10.1002/smll.201702156. View

16.

Perdew , Chevary , Vosko , Jackson , Pederson , Singh . Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys Rev B Condens Matter. 1992; 46(11):6671-6687. DOI: 10.1103/physrevb.46.6671. View

17.

Xie Y, Cai J, Wu Y, Zang Y, Zheng X, Ye J . Boosting Water Dissociation Kinetics on Pt-Ni Nanowires by N-Induced Orbital Tuning. Adv Mater. 2019; 31(16):e1807780. DOI: 10.1002/adma.201807780. View

18.

Chen L, Lu L, Zhu H, Chen Y, Huang Y, Li Y . Improved ethanol electrooxidation performance by shortening Pd-Ni active site distance in Pd-Ni-P nanocatalysts. Nat Commun. 2017; 8:14136. PMC: 5234093. DOI: 10.1038/ncomms14136. View

19.

Li T, Jing T, Jia X, Guo S, Li W, Yue H . Galvanic replacement mediated 3D porous PtCu nano-frames for enhanced ethylene glycol oxidation. Chem Commun (Camb). 2019; 55(96):14526-14529. DOI: 10.1039/c9cc06773f. View

20.

Yuan Y, Wang J, Adimi S, Shen H, Thomas T, Ma R . Zirconium nitride catalysts surpass platinum for oxygen reduction. Nat Mater. 2019; 19(3):282-286. DOI: 10.1038/s41563-019-0535-9. View