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/InGaN_(1-x)O_(x) nanowires s...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/InGaN_(1-x)O_(x) 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 photothermal synergy,the O atoms in Rh/InGaN_(1-x)O_(x) 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/InGaN_(1-x)O_(x) NWs nanoarchitecture thus demonstrates a measurable syngas evolution rate of 180.9 mmol g_(cat)^(-1) 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(ISI-XPS)and in-situ diffuse reflectance Fourier transform infrared spectroscopy characterizations,as well as density functional theory calculations reveal that under light illumination,Rh/InGaN_(1-x)O_(x) NWs facilitate releasing^(*)CH_(3) and H^(+)from CH_(4) by holes,followed by H_(2) evolution from H^(+)reduction with electrons.Subsequently,the O atoms in Rh/InGaN_(1-x)O_(x) can directly participate in CO generation by reacting with the ^(*)C species from CH_(4) dehydrogenation and contributes to the coke elimination,in concurrent formation of O vacancies.The resultant O vacancies are then replenished by CO_(2),showing an ideal chemical loop.This work presents a green strategy for syngas production via light-driven dry reforming of methane.展开更多
基金supported by the National Natural Science Foundation of China(22109095)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2022MS007)+4 种基金Shanghai Pilot Program for Basic Research-Shanghai Jiao Tong University(21TQ1400207)the National Key Research and Development Program of China(2023YFB4004900)Shanghai Municipal Science and Technology Major Projectsupported by the Natural Sciences and Engineering Research Council of Canada(NSERC)-RGPIN-2021-04250Centre Energie,Matériaux et Télécommunications,Institut National de la Recherche Scientifique(INRS)-Universitédu Québec.
文摘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/InGaN_(1-x)O_(x) 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 photothermal synergy,the O atoms in Rh/InGaN_(1-x)O_(x) 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/InGaN_(1-x)O_(x) NWs nanoarchitecture thus demonstrates a measurable syngas evolution rate of 180.9 mmol g_(cat)^(-1) 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(ISI-XPS)and in-situ diffuse reflectance Fourier transform infrared spectroscopy characterizations,as well as density functional theory calculations reveal that under light illumination,Rh/InGaN_(1-x)O_(x) NWs facilitate releasing^(*)CH_(3) and H^(+)from CH_(4) by holes,followed by H_(2) evolution from H^(+)reduction with electrons.Subsequently,the O atoms in Rh/InGaN_(1-x)O_(x) can directly participate in CO generation by reacting with the ^(*)C species from CH_(4) dehydrogenation and contributes to the coke elimination,in concurrent formation of O vacancies.The resultant O vacancies are then replenished by CO_(2),showing an ideal chemical loop.This work presents a green strategy for syngas production via light-driven dry reforming of methane.
