Faculty Publications
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Item Structure-sensitive electrocatalytic reduction of co2 to methanol over carbon-supported intermetallic ptzn nano-alloys(American Chemical Society service@acs.org, 2020) Payra, S.; Shenoy, S.; Chakraborty, C.; Tarafder, K.; Roy, S.The electrochemical reduction of CO2 (CO2RR) to produce valuable synthetic fuel like CH3OH not only mitigates the accumulated greenhouse gas from the environment but is also a promising direction toward attenuating our continuous reliance on fossil fuels. However, CO2RR to yield CH3OH suffers because of large overpotential, competitive H2 evolution reaction (HER), and poor product selectivity. In this regard, intermetallic alloy catalysts open up a wide possibility of fine-tuning the electronic property and attain appropriate structures that facilitate selective CO2RR. Here, we report for the first time the CO2RR over carbon-supported PtZn nano-alloys and probed the crucial role of structures and interfaces as active sites. PtZn/C, Pt3Zn/C, and PtxZn/C (1 < x < 3) synthesized from the metal-organic framework material were characterized structurally and morphologically. The catalysts demonstrated structure dependency toward CH3OH selectivity, as the mixed-phase PtxZn/C outperformed the phase-pure PtZn/C and Pt3Zn/C. The structure-dependent reaction mechanism and the kinetics were elucidated over the synthesized catalysts with the help of detail experiments and associated density functional theory calculations. Results showed that in spite of low electrochemically active surface area, PtxZn could not only have facilitated the single electron transfer to adsorbed CO2 but also showed better binding of the intermediate CO2 •- over its surface. Moreover, the lower bond energy between the mixed-phase surface and -OCH3 compared to the phase-pure catalysts has enabled higher CH3OH selectivity over PtxZn. This work opens a wide possibility of studying the role of interfaces between phase-pure nano-alloys toward CO2RR. © 2020 American Chemical SocietyItem Enhanced photocatalytic efficiency of layered CdS/CdSe heterostructures: Insights from first principles electronic structure calculations(Institute of Physics Publishing helen.craven@iop.org, 2020) Shenoy, S.; Tarafder, K.Metal sulfides are emerging as an important class of materials for photocatalytic applications, because of their high photo responsive nature in the wide visible light range. In this class of materials, CdS with a direct band gap of 2.4 eV, has gained special attention due to the relative position of its conduction band minimum, which is very close to the energies of the reduced protons. However, the photogenerated holes in the valence band of CdS are prone to oxidation and destroy its structure during photocatalysis. Thus constructing a CdS based heterostructure would be an effective strategy for improving the photocatalytic performance. In this work we have done a detail theoretical investigation based on hybrid density functional theory calculation to get insight into the energy band structure, mobility and charge transfer across the CdS/CdSe heterojunction. The results indicate that CdS/CdSe forms type-II heterostructure that has several advantages in improving the photocatalytic efficiency under visible light irradiation. © 2020 IOP Publishing Ltd.Item One-Dimensional Multichannel g-C3N4.7Nanostructure Realizing an Efficient Photocatalytic Hydrogen Evolution Reaction and Its Theoretical Investigations(American Chemical Society, 2021) Antil, B.; Kumar, L.; Ranjan, R.; Shenoy, S.; Tarafder, K.; Gopinath, C.S.; Deka, S.The emerging metal-free carbon nitride (C3N4) offers prominent possibilities for realizing the highly effective hydrogen evolution reaction (HER). However, its poor surface conductivity and insufficient catalytic sites hinder the HER performance. Herein, a one-dimensional vermicular rope-like graphitic carbon nitride nanostructure is demonstrated that consists of multichannel tubular pores and high nitrogen content, which is fabricated through a cost-effective approach having the final stoichiometry g-C3N4.7 for HER application. The present g-C3N4.7 is unique owing to the presence of abundant channels for the diffusion process, modulated surface chemistry with rich-electroactive sites from N-electron lone pairs, greatly reduced recombination rate of photoexcited exciton pairs, and a high donor concentration (4.26 × 1017 cm3). The catalyst offers a visible-light-driven photocatalytic H2 evolution rate as high as 4910 ? mol h-1 g-1 with an apparent quantum yield of 14.07% at band gap absorption (2.59 eV, 479 nm) under 7.68 mW cm-2 illumination. The number of hydrogen gas molecules produced is 1.307 × 1015 s-1 cm-2, which remained constant for a minimum of 18 h of repeated cycling in the HER without any degradation of the catalyst. In density functional theory calculations, a significant change in the band offset is observed due to N doping into the system in favor of electron catalysis. The theoretical band gap of a monolayer of g-C3N4.7 was enormously reduced because of the presence of additional densities of states from the doped N atom inside the band gap. These impurity or donor bands are formed inside the band gap region, which ultimately enhance the hydrogen ion reduction reaction enormously. © 2021 American Chemical Society.Item Bimetallic nanoparticles grafted ZnO hierarchical structures as efficient visible light driven photocatalyst: An experimental and theoretical study(Elsevier B.V., 2021) Shenoy, S.; Tarafder, K.; Sridharan, K.Bimetallic nanoparticles (NPs) exhibiting novel properties due to synergy between the individual elements have sparkled significant interest as a co-catalyst in enhancing the photocatalytic efficiency of semiconductor materials. Here, we report the photocatalytic activity of NiAg NPs embedded on hierarchical ZnO structures (NiAg-ZnO). Structural and morphological investigations through X-ray diffraction and scanning electron microscopy confirmed the formation of NiAg-ZnO. UV-Vis diffuse reflectance spectroscopy revealed the decrease in the bandgap energy of NiAg-ZnO (2.65 eV) in comparison to pristine ZnO (3.1 eV). Interestingly, the rate of photodegradation of methylene blue and rhodamine B dye molecules under visible light irradiation are two to three times enhanced with NiAg-ZnO in comparison to Ag-ZnO. Enhanced visible light absorption and effective charge separation due to the synergistic metal-semiconductor interface formed by the embedment of NiAg bimetallic NPs on ZnO led to the improved photocatalytic activity. Experimental results are further confirmed through the first principle electronic band structure calculations. © 2021