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-induced02437nas a2200253   4500008004100000022001400041245012400055210006900179260000800248300001400256490000700270520155500277653001801832653002101850653003001871653002201901653001701923100002201940700001901962700002701981700002802008700002502036856012202061       2022                        eng d  a1936-085100aPotential- and time-dependent dynamic nature of an oxide-derived pdin nanocatalyst during electrochemical CO2 reduction0 aPotential and timedependent dynamic nature of an oxidederived pd  cAPR  a6185-61960 v163 a<p>
	Electrochemical reduction of CO2 into valuable fuels and chemicals is a promising route of replacing fossil fuels by reducing CO2 emissions and minimizing its adverse effects on the climate. Tremendous efforts have been carried out for designing efficient catalyst materials to selectively produce the desired product in high yield from CO2 by the electrochemical process. In this work, a strategy is reported to enhance the electrochemical CO2 reduction reaction (ECO2RR) by constructing an interface between a metal-based alloy (PdIn) nanoparticle and an oxide (In2O3), which was synthesized by a facile solution method. The oxide-derived PdIn surface has shown excellent eCO(2)RR activity and enhanced CO selectivity with a Faradaic efficiency (FE) of 92.13% at -0.9 V (vs RHE). On the other hand, surface PdO formation due to charge transfer on the bare PdIn alloy reduces the CO2RR activity. With the support of in situ (EXAFS and IR) and ex situ (XPS, Raman) spectroscopic techniques, the optimum presence of the Pd-In-O interface has been identified as a crucial parameter for enhancing eCO(2)RR toward CO in a reducing atmosphere. The influence of eCO(2)RR duration is reported to affect the overall performance by switching the product selectivity from H-2 (from water reduction) to CO (from eCO(2)RR) on the oxide-derived alloy surface. This work also succeeded in the multifold enhancement of the current density by employing the gas diffusion electrode (GDE) and optimizing its process parameters in a flow cell configuration.</p>
10aCO2 reduction10aElectrochemistry10aheterostructure interface10ain situ mechanism10ananocatalyst1 aBagchi, Debabrata1 aSarkar, Shreya1 aSingh, Ashutosh, Kumar1 aVinod, Chathakudath, P.1 aPeter, Sebastian, C.  uhttps://library.ncl.res.in/content/potential-and-time-dependent-dynamic-nature-oxide-derived-pdin-nanocatalyst-during