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-sns2