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Title: High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

Abstract

The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5];  [2];  [2];  [2];  [2];  [3];  [4];  [6];  [2]; ORCiD logo [3];  [2]; ORCiD logo [5]
  1. Department of Chemistry and Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China; Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, U.K.
  2. Materials Science Divisions, Argonne National Laboratory, Lemont, Illinois 60439, United States
  3. Department of Chemistry and Key Laboratory of Organic Optoelectronics &, Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China
  4. Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States
  5. Department of Chemistry and Collaborative Innovation Center for Nanomaterial Science and Engineering, Tsinghua University, Beijing 100084, China
  6. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1412702
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 15
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Duan, Haohong, Li, Dongguo, Tang, Yan, He, Yang, Ji, Shufang, Wang, Rongyue, Lv, Haifeng, Lopes, Pietro P., Paulikas, Arvydas P., Li, Haoyi, Mao, Scott X., Wang, Chongmin, Markovic, Nenad M., Li, Jun, Stamenkovic, Vojislav R., and Li, Yadong. High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting. United States: N. p., 2017. Web. doi:10.1021/jacs.7b01376.
Duan, Haohong, Li, Dongguo, Tang, Yan, He, Yang, Ji, Shufang, Wang, Rongyue, Lv, Haifeng, Lopes, Pietro P., Paulikas, Arvydas P., Li, Haoyi, Mao, Scott X., Wang, Chongmin, Markovic, Nenad M., Li, Jun, Stamenkovic, Vojislav R., & Li, Yadong. High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting. United States. doi:10.1021/jacs.7b01376.
Duan, Haohong, Li, Dongguo, Tang, Yan, He, Yang, Ji, Shufang, Wang, Rongyue, Lv, Haifeng, Lopes, Pietro P., Paulikas, Arvydas P., Li, Haoyi, Mao, Scott X., Wang, Chongmin, Markovic, Nenad M., Li, Jun, Stamenkovic, Vojislav R., and Li, Yadong. Wed . "High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting". United States. doi:10.1021/jacs.7b01376.
@article{osti_1412702,
title = {High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting},
author = {Duan, Haohong and Li, Dongguo and Tang, Yan and He, Yang and Ji, Shufang and Wang, Rongyue and Lv, Haifeng and Lopes, Pietro P. and Paulikas, Arvydas P. and Li, Haoyi and Mao, Scott X. and Wang, Chongmin and Markovic, Nenad M. and Li, Jun and Stamenkovic, Vojislav R. and Li, Yadong},
abstractNote = {The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.},
doi = {10.1021/jacs.7b01376},
journal = {Journal of the American Chemical Society},
number = 15,
volume = 139,
place = {United States},
year = {Wed Apr 05 00:00:00 EDT 2017},
month = {Wed Apr 05 00:00:00 EDT 2017}
}
  • Search for active, stable and cost-efficient electrocatalysts for hydrogen production via water splitting could make substantial impact to the energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high surface area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) compared to Rh/C and Pt/C catalysts. The atomic structure of the rhodium phosphide nanocubes was directly observed by annular dark-field scanning transmission electron microscopy (ADF-STEM),more » which revealed phosphorous-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorous plays crucial role in determining the robust catalyst properties.« less
  • Exploring nonprecious metal electrocatalysts to replace the noble metal-based catalysts for full water electrocatalysis is still an ongoing challenge. In this work, porous structured ternary nickel–iron–phosphide (Ni–Fe–P) nanocubes were synthesized through one-step phosphidation of a Ni–Fe-based Prussian blue analogue. The Ni–Fe–P nanocubes exhibit a rough and loose porous structure on their surface under suitable phosphating temperature, which is favorable for the mass transfer and oxygen diffusion during the electrocatalysis process. As a result, Ni–Fe–P obtained at 350 °C with poorer crystallinity offers more unsaturated atoms as active sites to expedite the absorption of reactants. Additionally, the introduction of nickel improvedmore » the electronic structure and then reduced the charge-transfer resistance, which would result in a faster electron transport and an enhancement of the intrinsic electrocatalytic activities. Benefiting from the unique porous nanocubes and the chemical composition, the Ni–Fe–P nanocubes exhibit excellent hydrogen evolution reaction and oxygen evolution reaction activities in alkaline medium, with low overpotentials of 182 and 271 mV for delivering a current density of 10 mA cm–2, respectively. Moreover, the Ni–Fe–P nanocubes show outstanding stability for sustained water splitting in the two-electrode alkaline electrolyzer. Furthermore, this work not only provides a facile approach for designing bifunctional electrocatalysts but also further extends the application of metal–organic frameworks in overall water splitting.« less
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  • The rising H 2 economy demands active and durable electrocatalysts based on low-cost, earth-abundant materials for water electrolysis/photolysis. Here we report nanoscale Ni metal cores over-coated by a Cr 2O 3-blended NiO layer synthesized on metallic foam substrates. The Ni@NiO/Cr 2O 3 triphase material exhibits superior activity and stability similar to Pt for the hydrogen-evolution reaction in basic solutions. The chemically stable Cr 2O 3 is crucial for preventing oxidation of the Ni core, maintaining abundant NiO/Ni interfaces as catalytically active sites in the heterostructure and thus imparting high stability to the hydrogen-evolution catalyst. The highly active and stable electrocatalystmore » enables an alkaline electrolyzer operating at 20 mA cm –2 at a voltage lower than 1.5 V, lasting longer than 3 weeks without decay. Thus, the non-precious metal catalysts afford a high efficiency of about 15 % for light-driven water splitting using GaAs solar cells.« less
  • Hydrogenases are a diverse group of metalloenzymes which catalyze the reversible conversion between molecular hydrogen and protons at high rates. The catalytic activity of these enzymes does not require overpotential because their active site has been evolutionarily optimized to operate fast and efficiently. These enzymes have inspired the development of molecular catalysts, which have dramatically improved in efficiency in recent years, to the point that some synthetic catalysts even outperform hydrogenases under certain conditions. In this work, we use a reversible noble-metal-free homogeneous catalyst, the [Ni(PCy2NPhe2)2]2+ complex, and we covalently immobilize it on a functionalized highly oriented pyrolytic graphite “edge”more » (HOPGe) electrode surface. This catalyst is not water soluble, but once it is surface-confined on the electrode, it maintains its catalytic properties in aqueous solutions, showing reversibility for H2 oxidation/reduction. Immobilization of the [Ni(PCy2NPhe2)2]2+ complex onto a multi-walled carbon nanotubes coated electrode leads to even higher catalytic current densities and enhanced stability.« less
  • Cited by 4