Abstract
Light-driven dry reforming of methane toward syngas presents a proper solution for alleviating climate change and for the sustainable supply of transportation fuels and chemicals.Herein,Rh/InGaN1-xOx nanowires supported by silicon wafer are explored as an ideal platform for loading Rh nanoparticles,thus assembling a new nanoarchitecture for this grand topic.In combination with the remarkable photo-thermal synergy,the O atoms in Rh/InGaN1-xOx can significantly lower the apparent activation energy of dry reforming of methane from 2.96 eV downward to 1.70 eV.The as-designed Rh/InGaN1-xOx NWs nanoarchitecture thus demonstrates a measurable syngas evolution rate of 180.9 mmol g-1cat h-1 with a marked selectivity of 96.3％under concentrated light illumination of 6 W cm-2.What is more,a high turnover number(TON)of 4182 mol syngas per mole Rh has been realized after six reuse cycles without obvious activity degradation.The correlative 18O isotope labeling experiments,in-situ irradiated X-ray photoelectron spectroscopy(1SI-XPS)and in-situ diffuse reflectance Fourier transform infrared spec-troscopy characterizations,as well as density functional theory calculations reveal that under light illu-mination,Rh/InGaN1-xOx NWs facilitate releasing *CH3 and H+from CH4 by holes,followed by H2 evolution from H+reduction with electrons.Subsequently,the O atoms in Rh/InGaN1-xOx can directly participate in CO generation by reacting with the *C species from CH4 dehydrogenation and contributes to the coke elimination,in concurrent formation of O vacancies.The resultant O vacancies are then replenished by CO2,showing an ideal chemical loop.This work presents a green strategy for syngas pro-duction via light-driven dry reforming of methane.
基金项目
国家自然科学基金(22109095)
Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2022MS007)
Shanghai Pilot Program for Basic Research-Shanghai Jiao Tong University(21TQ1400207)
国家重点研发计划(2023YFB4004900)
Shanghai Municipal Science and Technology Major Project()
加拿大自然科学与工程研究委员会项目(RGPIN-2021-04250)
Centre Energie,Matériaux et Télécommunications,Institut National de la Recherche Scientifique(INRS)-Université du Québec()
NETL
NSTL
万方数据