Enhancement of NH3 Production in Electrochemical N2 Reduction by the Cu-Rich Inner Surfaces of Beveled CuAu Nanoboxes

Biva Talukdar; Tung-Chun Kuo; Brian T Sneed; Lian-Ming Lyu; Hung-Min Lin; Yu-Chun Chuang; Mu-Jeng Cheng; Chun-Hong Kuo

doi:10.1021/acsami.1c03454

Enhancement of NH₃ Production in Electrochemical N₂ Reduction by the Cu-Rich Inner Surfaces of Beveled CuAu Nanoboxes

ACS Appl Mater Interfaces. 2021 Nov 10;13(44):51839-51848. doi: 10.1021/acsami.1c03454. Epub 2021 Apr 12.

Authors

Biva Talukdar^{1

2

3}, Tung-Chun Kuo⁴, Brian T Sneed⁵, Lian-Ming Lyu⁶, Hung-Min Lin^{1

7}, Yu-Chun Chuang⁸, Mu-Jeng Cheng⁴, Chun-Hong Kuo^{1

9}

Affiliations

¹ Institute of Chemistry, Academia Sinica, Taipei 11529, Taiwan.
² Sustainable Chemical Science and Technology, Taiwan International Graduate Program, Academia Sinica and National Yang Ming Chiao Tung University, Taipei 11529, Taiwan.
³ Department of Applied Chemistry, National Yang Ming Chiao Tung University, Hsinchu 30010, Taiwan.
⁴ Department of Chemistry, National Cheng Kung University, Tainan 70101, Taiwan.
⁵ Cabot Microelectronics, Aurora, Illinois 60504, United States.
⁶ Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan.
⁷ Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
⁸ National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.
⁹ Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan.

PMID: 33845573
DOI: 10.1021/acsami.1c03454

Abstract

The global ammonia yield is critical to the fertilizer industry as the global food demand is highly dependent on it, whereas, NH₃ is also a key chemical for pharmaceutical, textile, plastic, explosive, and dye-making industries. At present, the demand for NH₃ is fulfilled by the Haber-Bosch method, which consumes 1-3% of global energy and causes 0.5-1% CO₂ emission every year. To reduce emissions and improve energy efficiency, the electrochemical nitrogen gas reduction reaction (N₂RR) has received much attention and support after the funding announcement by the U.S. Department of Energy. In this work, we have created hollow CuAu nanoboxes with Cu-rich inner walls to improve the NH₃ Faradaic efficiency in N₂RR. These beveled nanoboxes are produced in different degrees of corner and edge etching, which produces both polyhedral and concave structures. In N₂RR, the binary CuAu nanoboxes enhanced NH₃ production compared to individual Au and Cu nanocubes. The results of DFT calculations suggest the Cu-rich inner walls in the hollow beveled CuAu nanoboxes play a major role in their performance by reducing the free energy ΔG_*NNH for the potential-determining step to form *NNH (* + N₂(g) + H⁺ + e^- → *NNH). Meanwhile, the results in 10-cycle and solar-illuminated N₂RR indicate the beveled CuAu nanoboxes are not only robust electrocatalysts but show promise in photocatalysis as well.

Keywords: alloy; bimetallic; copper; gold; nanobox.

Publication types

Review