Employing sun energy for chemical bond activation by “Hot Electrons” of plasmonic black gold-nickel Rishi Verma, Vivek Polshettiwar Tata Institute of fundamental Research, India The development of localized surface plasmon resonance (LSPR) has made it possible to use solar light to catalyze previously difficult reactions 1,2 . Large numbers of short-lived hot charge carriers that catalyze chemical processes are produced on the surface of the nanoparticle after the decay of the LSPR excitation. As a consequence, novel and targeted reaction pathways that were not feasible with conventional heat catalysis are discovered. For efficient light absorption and catalytic activity, the photocatalyst should absorb the whole solar broadband spectrum. Dendritic plasmonic colloidosomes (DPC-C4) 3 , commonly known as "black gold," a recently discovered novel material from our group, might be a fantastic option. Black gold absorbs all visible and near-infrared light due to its heterogeneous particle size distribution and interparticle lengths of Au nanoparticles on nanosilica (DFNS) 4,5 . In this work, we have synthesized black gold loaded with nickel sites (DPC-C4-Ni). Under light excitation, DPC- C4-Ni excel over DPC-C4 and DFNS-Ni in terms of photocatalytic CO 2 hydrogenation activities. DPC-C4-Ni shows a very high photocatalytic CO production rate (2464 ± 40 mmol g Ni -1 h -1 ) with 95 % CO selectivity. Notably, the reaction was carried out in a flow reactor at low temperature and atmospheric pressure without external heating. The photocatalyst was stable for 100 h. The photocatalytic CO 2 hydrogenation reaction mechanism was further explored by using i) finite-difference time-domain simulations (FDTD), ii) light intensity-dependent production rate, and iii) in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study. DRIFTS indicated the direct dissociation of CO 2 as the CO 2 hydrogenation mechanism via linearly bonded Ni-CO intermediates. References 1. Verma, R., Belgamwar, R., Polshettiwar, V. Plasmonic Photocatalysis for CO 2 Conversion to Chemicals and Fuels. ACS Mater. Lett. 3 , 574–598 (2021). 2. Aslam, U., Rao, V. G., Chavez, S., Linic, S. Catalytic conversion of solar to chemical energy on plasmonic metal nanostructures. Catal. 1 , 656-665 (2018) 3. Dhiman, M., Maity, A., Das, A., Belgamwar, R., Chalke, B., Lee, Y., Sim, K., Nam, J. –M., Polshettiwar, V. Plasmonic colloidosomes of black gold for solar energy harvesting and hotspots directed catalysis for CO 2 to fuel conversion. Sci. 10 , 6594-6603 (2019). 4. Maity, A., Belgamwar, R., Polshettiwar, V. Facile synthesis to tune size, textural properties and fiber density of dendritic fibrous nanosilica for applications in catalysis and CO 2 Nat. Protoc. 14 , 2177-224 (2019). 5. Polshettiwar, V. Dendritic Fibrous Nano-Silica (DFNS): Discovery, Synthesis, Formation Mechanism, Catalysis, and CO 2 Capture-Conversion. ACS Accounts of Chemical Research , 55 , 1395–1410 (2022).
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