02500nas a2200301   4500008004100000022001400041245012000055210006900175260000900244300001200253490000700265520151200272653001801784653002001802653001201822653001901834653001301853100001501866700001901881700001801900700002801918700002201946700002001968700002801988700002702016700002502043856013002068       2022                        eng d  a2155-543500aNoble-metal-free heterojunction photocatalyst for selective CO2 reduction to methane upon induced strain relaxation0 aNoblemetalfree heterojunction photocatalyst for selective CO2 re  cJAN   a687-6970 v123 a<p>
	Sunlight-driven CO2 hydrogenation has drawn tremendous attention. However, selective CH4 formation via CO2 photoreduction is very challenging. Herein, we report a metal oxide semiconductor heterojunction consisting of BiVO4 and WO3 as a photocatalyst for the efficient conversion of carbon dioxide (CO2) selectively to methane (105 mu mol g(-1) h(-1)) under visible light in the absence of a sacrificial agent. Wise selection of the reaction medium and the strategically tuned heterojunction upon strain relaxation suppresses the competitive hydrogen generation reaction. The detailed photophysical, photoelectrochemical, and X-ray absorption spectroscopy studies pointed to the Z-scheme mechanism of electron transfer, which favors superior electron and hole separation compared to the individual components of the composite catalyst and other well-known photocatalysts reported for CO2 reduction. The observations are further corroborated by experimental diffuse reflectance infrared Fourier transform spectroscopy and theoretical density-functional theory calculations, which reveal that the heterojunction has a lower free-energy barrier for CO2 conversion to CH4 due to the larger stabilization of the *CH2O intermediate on the strain-relaxed heterojunction surface, in comparison to the pristine BiVO4 surface. The present work provides fundamental insights for constructing high-performance heterojunction photocatalysts for the selective conversion of CO2 to desired chemicals and fuels.</p>
10aCO2 reduction10aheterostructure10amethane10aPhotocatalysis10aZ-scheme1 aDas, Risov1 aSarkar, Shreya1 aKumar, Ritesh1 aRamarao, Seethiraju, D.1 aCherevotan, Arjun1 aJasil, Mohammed1 aVinod, Chathakudath, P.1 aSingh, Abhishek, Kumar1 aPeter, Sebastian, C.  uhttps://library.ncl.res.in/content/noble-metal-free-heterojunction-photocatalyst-selective-co2-reduction-methane-upon-induced