Prediction of a low-temperature N2 dissociation catalyst exploiting near-IR-to-visible light nanoplasmonics

Science Advances
John Mark P Martirez, Emily A Carter

Abstract

Despite more than a century of advances in catalyst and production plant design, the Haber-Bosch process for industrial ammonia (NH3) synthesis still requires energy-intensive high temperatures and pressures. We propose taking advantage of sunlight conversion into surface plasmon resonances in Au nanoparticles to enhance the rate of the N2 dissociation reaction, which is the bottleneck in NH3 production. We predict that this can be achieved through Mo doping of the Au surface based on embedded multireference correlated wave function calculations. The Au component serves as a light-harvesting antenna funneling energy onto the Mo active site, whereby excited-state channels (requiring 1.4 to 1.45 eV, near-infrared-to-visible plasmon resonances) may be accessed. This effectively lowers the energy barriers to 0.44 to 0.77 eV/N2 (43 to 74 kJ/mol N2) from 3.5 eV/N2 (335 kJ/mol N2) in the ground state. The overall process requires three successive surface excitation events, which could be facilitated by amplified resonance energy transfer due to plasmon local field enhancement.

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Citations

Jul 25, 2018·Advanced Materials·Jianhua YangJianfang Wang
Apr 3, 2021·ACS Applied Materials & Interfaces·Guokui ZhengLiang Chen
Dec 4, 2020·Annual Review of Physical Chemistry·John Mark P MartirezEmily A Carter
Apr 23, 2021·Physical Chemistry Chemical Physics : PCCP·Geert-Jan Kroes
Nov 9, 2019·Journal of the American Chemical Society·Jing ZhangJun Lou
May 12, 2021·Proceedings of the National Academy of Sciences of the United States of America·Linan ZhouNaomi J Halas
Jun 8, 2021·Journal of Chemical Theory and Computation·John Mark P Martirez, Emily A Carter
Aug 20, 2019·Accounts of Chemical Research·Zhenglong ZhangHongxing Xu
Aug 21, 2019·Accounts of Chemical Research·Julian GargiuloEmiliano Cortés
Oct 5, 2018·Journal of the American Chemical Society·Chongyi LingJinlan Wang
Dec 8, 2021·ACS Applied Materials & Interfaces·Tong MouBin Wang

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Methods Mentioned

BETA
surface plasmon resonances

Software Mentioned

Vienna Ab initio Simulation Package ( VASP )
DFT
emb
CAS
Molpro
NEVPT2
SA
VASP

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