[EN] The rational design and in deep understanding of efficient, affordable and stable materials to promote the light-assisted production of fuels and commodity chemicals is very appealing for energy crisis and climate ...[+]
[EN] The rational design and in deep understanding of efficient, affordable and stable materials to promote the light-assisted production of fuels and commodity chemicals is very appealing for energy crisis and climate change amelioration. Herein, we have prepared a series of Co-doped hydroxyapatite (HAP) catalysts with different Co content. The materials structure has been widely investigated by XRD, FT-IR, HRTEM, XPS, XAS, as well as computational simulations based on Density Functional Theory (DFT) with PBE functional. At low Co loading, there is a partial substitution of Ca cations in the HAP structure, while higher loadings promote the precipitation of small (similar to 2 nm) Co nanoparticles on the HAP surface. For the optimal Co content, a constant CO rate of 62 mmol center dot g(-1)center dot h(-1) at 1 sun illumination and 400 degrees C, with the material being stable for 90 h. Visible and NIR photons have been determined responsible of the light-assisted activity enhanced. Mechanistic studies based on both experimental and DFT simulations show that H-2 preferentially adsorbs to metallic Co, while CO2 adsorbs to the HAP surface oxygen. Moreover, both direct photo- and plasmon-driven contributions have been separated in order to study their mechanisms independently.[-]
info:eu-repo/grantAgreement/EC/H2020/861151/EU info:eu-repo/grantAgreement/AEI//PID2021-126071OB-C21//APLICANDO MXENOS COMO CATALIZADORES DEFINITIVOS PARA LA PRODUCCIÓN DE COMBUSTIBLES SOLARES/ info:eu-repo/grantAgreement/EC/H2020/862453/EU info:eu-repo/grantAgreement/AGENCIA ESTATAL DE INVESTIGACION//CEX2021-001230-S//CENTRO DE EXCELENCIA SEVERO OCHO INSTITUTO DE TECNOLOGIA QUIMICA (ITQ)/ info:eu-repo/grantAgreement/GVA//PROMETEO%2F2021%2F038/ info:eu-repo/grantAgreement/GVA//MFA-2022-023/ info:eu-repo/grantAgreement/AEI//CEX2019-000925-S/ info:eu-repo/grantAgreement/MICINN//PLEC2021-7831/ info:eu-repo/grantAgreement/MICINN//RYC2021-031006-I/ info:eu-repo/grantAgreement/MICINN//PID2021-122515OB-I00/ [-]
Thanks:
Financial support by European Comission (FlowPhotoChem Grant Agreement 862453 and Solar2Chem grant agreement 861151), The Spanish Ministry of Science and Innovation (Severo Ochoa CEX2021-1230-S financed by MCIN/AEI/10.13 ...[+]
Financial support by European Comission (FlowPhotoChem Grant Agreement 862453 and Solar2Chem grant agreement 861151), The Spanish Ministry of Science and Innovation (Severo Ochoa CEX2021-1230-S financed by MCIN/AEI/10.13039/501100011033, PDI2021-126071-OB-C21 financed by MCIN/AEI/10.13039/501100011033 and by FEDER "Una manera de hacer Europa", and PLEC2021-7831 financed by MCIN/AEI/10.13039/501100011033 and by European Union Next-Generation EU/PRTR), and Generalitat Valenciana (Prometeu 2021-038 and MFA-2022-023 financed by European Union-Next Generation EU, through the Conselleria de Innovacion, Universidades, Ciencia y Sociedad Digital) are gratefully acknowledged. J. A. thanks the Spanish Ministry of Science and Innovation for a Ramon y Cajal research associate contract (RYC2021-031006-I) financed by MCIN/AEI/10.13039/501100011033 and by European Union/Next Generation EU/PRTR). P. N. and N. L. thank the Spanish Ministry of Science and Innovation for financial support PID2021-122515OB-I00, and Severo Ochoa Grant MCIN/AEI/10.13039/501100011033 CEX2019-000925-S) and Barcelona Supercomputing Center-MareNostrum (BSC-RES) for providing generaous computational resources.[-]