02957nas a2200265   4500008004100000022001400041245015500055210006900210260000800279300001600287490000800303520201000311100002602321700001702347700002802364700001702392700002102409700002102430700002102451700001802472700003202490700001702522700002502539856012702564       2026                        eng d  a0002-786300aSelectivity reversal from CO to ethylene products in CO2 photoreduction via electronic modulation of SnS2 using a vinyl-bridged porous organic polymer0 aSelectivity reversal from CO to ethylene products in CO2 photore  cJUL  a25669-256840 v1483 a<p>
	Developing an efficient and robust photocatalyst for optimal C2+ product generation from carbon dioxide (CO2) is a pressing need in advancing solar fuel production. In this study, we designed an ionic vinylene-bridged conjugated porous organic polymer (Py-POP) enriched with charged pyridine groups via a quaternization-promoted Knoevenagel condensation reaction. The resulting positively charged polymeric framework with shape-persistent nanochannels enabled the uniform assembly of SnS2 units through ionic interactions mediated by amino and sulfhydryl groups. The hybrid porous photopolymer (SnS2@Py-POP) converts CO2 into ethylene with a rate of 34.7 mu mol g-1 h-1 with a selectivity of ethylene around 78.7% under visible light photoirradiation, which outperforms all the C2 selective Sn-based photocatalysts. Our findings principally sheds light on the mechanism of selectivity reversal (from C1 to C2 product) by hybrid catalyst framework engineering. In-depth investigations by synchrotron-based X-ray absorption spectroscopy (XAS) and morphological analysis via high-resolution transmission electron microscopy (HRTEM) reveal the nature of interaction for hybrid heterostructure formation within the porous network. Electron transfer pathways were mapped using time-resolved photoluminescence (TRPL) and transient absorption spectroscopy (TAS), which revealed a Z-scheme electron transfer mechanism. This mechanism facilitates enhanced electron accumulation on the SnS2 layer, promoting efficient CO2 activation and subsequent C-C coupling, ultimately leading to ethylene formation. Furthermore, the ethylene formation mechanism has been investigated in detail by time-resolved diffuse reflectance infrared spectroscopy (TR-DRIFTS), corroborated with density functional theory (DFT). This study opens a new avenue for achieving selectivity reversal in a C1 selective photocatalyst through electronic modulation enabled by the formation of an inorganic-organic hybrid heterostructure.</p>
1 aChakraborty, Subhajit1 aBoro, Bishal1 aNavodye, S., A. Keishan1 aGhosh, Rajib1 aShrotri, Abhijit1 aUrkude, Rajashri1 aChawla, Geetansh1 aVinod, C., P.1 aGunasooriya, G., T. Kasun K1 aMondal, John1 aPeter, Sebastian, C.  uhttps://library.ncl.res.in/content/selectivity-reversal-co-ethylene-products-co2-photoreduction-electronic-modulation-sns202592nas a2200349   4500008004100000022001400041245013300055210006900188260000900257300001600266490000700282520142600289653002501715653003101740653002501771653002701796653002301823100002201846700002001868700002001888700002101908700002001929700002101949700002701970700001701997700002102014700001802035700002202053700001602075700002502091856012602116       2026                        eng d  a2155-543500aUnraveling the mechanism of higher alcohol production on the ordered PdCu3 nanointermetallic surface during CO2 electroreduction0 aUnraveling the mechanism of higher alcohol production on the ord  cJUL   a12486-125040 v163 a<p>
	For advancing electrochemical CO2 reduction, it is crucial to design efficient catalysts with high activity and selectivity for a particular product. Engineering structure at the atomic level by controlled synthesis strategies can effectively tune the product selectivity by optimizing the binding energy of the key intermediates involved in the reaction. Here, we demonstrate a morphology-controlled (spherical and cubic) synthesis route for PdCu3-ordered intermetallic nanoparticles without using any external strong reducing agent. Structurally ordered cubic PdCu3 with predominantly (100) facets exhibits higher selectivity for ethanol (Faradaic efficiency (FE): 44.2%) and n-propanol (FE: 17.0%; formation rate: 39.99 mu mol h(-1) cm(-2) mg(-1)) from CO2 compared to spherical PdCu3 with (111) facets (ethanol FE: 32.7%; n-propanol FE: 9.46%). Incorporating the electrode-electrolyte interactions, the ab initio calculations highlight the key C-C coupling step enabling the formation of C2+ products. The active Pd sites, depending on their presence and absence on the surface of PdCu3 (100) facets, significantly influence the C-C coupling barrier by controlling CO* and OCCOH* binding. In contrast, this barrier remains unaffected on (111) facets due to the Pd arrangement. This further establishes the important role of alloying Pd with Cu in rationally tailored surfaces for higher alcohol synthesis.</p>
10aCO2 electroreduction10ahigher alcohol selectivity10aIn situ spectroscopy10aintermetallic catalyst10arole of morphology1 aBagchi, Debabrata1 aIyer, Jayendran1 aKhan, Tuhin, S.1 aChawla, Geetansh1 aDutta, Nilutpal1 aGiri, Bishnubasu1 aSingh, Ashutosh, Kumar1 aSaha, Saurav1 aKaur, Komalpreet1 aVinod, C., P.1 aGautam, Ujjal, K.1 aHaider, Ali1 aPeter, Sebastian, C.  uhttps://library.ncl.res.in/content/unraveling-mechanism-higher-alcohol-production-ordered-pdcu3-nanointermetallic-surface