Bimetallic Nickel-molybdenum/tungsten Nanoalloys for High-efficiency Hydrogen Oxidation Catalysis in Alkaline Electrolytes

Overview

Journal Nat Commun

Specialty Biology

Date 2020 Sep 23

PMID 32963247

Citations 24

Authors

Yu Duan

Zi-You Yu

Li Yang

Li-Rong Zheng

Chu-Tian Zhang

Xiao-Tu Yang

Fei-Yue Gao

Xiao-Long Zhang

Xingxing Yu

Ren Liu

Hong-He Ding

Chao Gu

Xu-Sheng Zheng

Lei Shi

Jun Jiang

Jun-Fa Zhu

Min-Rui Gao

Shu-Hong Yu

Affiliations

Soon will be listed here.

Abstract

Hydroxide exchange membrane fuel cells offer possibility of adopting platinum-group-metal-free catalysts to negotiate sluggish oxygen reduction reaction. Unfortunately, the ultrafast hydrogen oxidation reaction (HOR) on platinum decreases at least two orders of magnitude by switching the electrolytes from acid to base, causing high platinum-group-metal loadings. Here we show that a nickel-molybdenum nanoalloy with tetragonal MoNi phase can catalyze the HOR efficiently in alkaline electrolytes. The catalyst exhibits a high apparent exchange current density of 3.41 milliamperes per square centimeter and operates very stable, which is 1.4 times higher than that of state-of-the-art Pt/C catalyst. With this catalyst, we further demonstrate the capability to tolerate carbon monoxide poisoning. Marked HOR activity was also observed on similarly designed WNi catalyst. We attribute this remarkable HOR reactivity to an alloy effect that enables optimum adsorption of hydrogen on nickel and hydroxyl on molybdenum (tungsten), which synergistically promotes the Volmer reaction.

Citing Articles

Formation Mechanism and Influencing Factors of Micro-Nano Dual-Size NiPd Alloy with a Flake-like Microstructure.

Zhao H, Xiao W, Liu D, Zhao W, Zhou K, Hou L Materials (Basel). 2025; 18(4).

PMID: 40004351 PMC: 11857633. DOI: 10.3390/ma18040829.

Facilitating alkaline hydrogen evolution kinetics via interfacial modulation of hydrogen-bond networks by porous amine cages.

Zhou S, Cao W, Shang L, Zhao Y, Xiong X, Sun J Nat Commun. 2025; 16(1):1849.

PMID: 39984442 PMC: 11845474. DOI: 10.1038/s41467-025-56962-z.

All-round enhancement induced by oxophilic single Ru and W atoms for alkaline hydrogen oxidation of tiny Pt nanoparticles.

Jiao W, Ren Z, Cui Z, Ma C, Shang Z, Chen G Nat Commun. 2025; 16(1):883.

PMID: 39837847 PMC: 11750993. DOI: 10.1038/s41467-025-56240-y.

Yttrium-doped NiMo-MoO heterostructure electrocatalysts for hydrogen production from alkaline seawater.

Liu S, Zhang Z, Dastafkan K, Shen Y, Zhao C, Wang M Nat Commun. 2025; 16(1):773.

PMID: 39824853 PMC: 11742019. DOI: 10.1038/s41467-025-55856-4.

The Impact of Metal-Support Interaction on the Structure and Activity of Carbon-Supported Ni Nanoparticle Catalysts for Alkaline Hydrogen Oxidation Reaction.

Akamine Y, Nishino F, Yamashita T, Tsushida M, Awaya K, Machida M ACS Appl Mater Interfaces. 2024; 16(50):69316-69323.

PMID: 39645609 PMC: 11660032. DOI: 10.1021/acsami.4c15120.

References

Ohyama J, Sato T, Yamamoto Y, Arai S, Satsuma A . Size specifically high activity of Ru nanoparticles for hydrogen oxidation reaction in alkaline electrolyte. J Am Chem Soc. 2013; 135(21):8016-21. DOI: 10.1021/ja4021638. View

Qiu Y, Xin L, Li Y, McCrum I, Guo F, Ma T . BCC-Phased PdCu Alloy as a Highly Active Electrocatalyst for Hydrogen Oxidation in Alkaline Electrolytes. J Am Chem Soc. 2018; 140(48):16580-16588. DOI: 10.1021/jacs.8b08356. View

Lu S, Zhuang Z . Investigating the Influences of the Adsorbed Species on Catalytic Activity for Hydrogen Oxidation Reaction in Alkaline Electrolyte. J Am Chem Soc. 2017; 139(14):5156-5163. DOI: 10.1021/jacs.7b00765. View

Zhuang Z, Giles S, Zheng J, Jenness G, Caratzoulas S, Vlachos D . Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte. Nat Commun. 2016; 7:10141. PMC: 4735558. DOI: 10.1038/ncomms10141. View

Chattot R, Le Bacq O, Beermann V, Kuhl S, Herranz J, Henning S . Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis. Nat Mater. 2018; 17(9):827-833. PMC: 6109589. DOI: 10.1038/s41563-018-0133-2. View

Maximoff S, Ernzerhof M, Scuseria G . Current-dependent extension of the Perdew-Burke-Ernzerhof exchange-correlation functional. J Chem Phys. 2004; 120(5):2105-9. DOI: 10.1063/1.1634553. View

Sheng W, Zhuang Z, Gao M, Zheng J, Chen J, Yan Y . Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy. Nat Commun. 2015; 6:5848. DOI: 10.1038/ncomms6848. View

Li B, Wang X, Wu X, He G, Xu R, Lu X . Phase and morphological control of MoO nanostructures for efficient cancer theragnosis therapy. Nanoscale. 2017; 9(31):11012-11016. DOI: 10.1039/c7nr03469e. View

Alia S, Pivovar B, Yan Y . Platinum-coated copper nanowires with high activity for hydrogen oxidation reaction in base. J Am Chem Soc. 2013; 135(36):13473-8. DOI: 10.1021/ja405598a. View

10.

Okubo K, Ohyama J, Satsuma A . Surface modification of Pt nanoparticles with other metals boosting the alkaline hydrogen oxidation reaction. Chem Commun (Camb). 2019; 55(21):3101-3104. DOI: 10.1039/c9cc00582j. View

11.

Setzler B, Zhuang Z, Wittkopf J, Yan Y . Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells. Nat Nanotechnol. 2016; 11(12):1020-1025. DOI: 10.1038/nnano.2016.265. View

12.

Kundu M, Bhowmik T, Mishra R, Barman S . Platinum Nanostructure/Nitrogen-Doped Carbon Hybrid: Enhancing its Base Media HER/HOR Activity through Bi-functionality of the Catalyst. ChemSusChem. 2018; 11(14):2388-2401. DOI: 10.1002/cssc.201800856. View

13.

Chen Z, Song Y, Cai J, Zheng X, Han D, Wu Y . Tailoring the d-Band Centers Enables Co N Nanosheets To Be Highly Active for Hydrogen Evolution Catalysis. Angew Chem Int Ed Engl. 2018; 57(18):5076-5080. DOI: 10.1002/anie.201801834. View

14.

Li J, Ghoshal S, Bates M, Miller T, Davies V, Stavitski E . Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media. Angew Chem Int Ed Engl. 2017; 56(49):15594-15598. DOI: 10.1002/anie.201708484. View

15.

Mao J, Chen W, He D, Wan J, Pei J, Dong J . Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation. Sci Adv. 2017; 3(8):e1603068. PMC: 5576877. DOI: 10.1126/sciadv.1603068. View

16.

Wang L, Mahoney E, Zhao S, Yang B, Chen J . Low loadings of platinum on transition metal carbides for hydrogen oxidation and evolution reactions in alkaline electrolytes. Chem Commun (Camb). 2016; 52(18):3697-700. DOI: 10.1039/c5cc10439d. View

17.

Ni W, Krammer A, Hsu C, Ming Chen H, Schuler A, Hu X . Ni N as an Active Hydrogen Oxidation Reaction Catalyst in Alkaline Medium. Angew Chem Int Ed Engl. 2019; 58(22):7445-7449. DOI: 10.1002/anie.201902751. View

18.

Zhang J, Wang T, Liu P, Liao Z, Liu S, Zhuang X . Efficient hydrogen production on MoNi electrocatalysts with fast water dissociation kinetics. Nat Commun. 2017; 8:15437. PMC: 5442356. DOI: 10.1038/ncomms15437. View

19.

Tian X, Zhao P, Sheng W . Hydrogen Evolution and Oxidation: Mechanistic Studies and Material Advances. Adv Mater. 2019; 31(31):e1808066. DOI: 10.1002/adma.201808066. View

20.

Liu E, Li J, Jiao L, Doan H, Liu Z, Zhao Z . Unifying the Hydrogen Evolution and Oxidation Reactions Kinetics in Base by Identifying the Catalytic Roles of Hydroxyl-Water-Cation Adducts. J Am Chem Soc. 2019; 141(7):3232-3239. DOI: 10.1021/jacs.8b13228. View