Faculty Publications
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Item Cadmium sulfide nanostructures: Influence of morphology on the photocatalytic degradation of erioglaucine and hydrogen generation(Elsevier B.V., 2019) Shenoy, S.; Jang, E.; Park, T.J.; Gopinath, C.S.; Sridharan, K.Size and shape of inorganic materials are known to have great effects on their physical and chemical properties. Here, for the first time we report the visible light driven photocatalytic degradation of erioglaucine – a stable organic dye molecule in the presence of chemically synthesized nanoscale CdS with 1D (nanorods), 2D (nanosheets) and 3D (hierarchical) morphology. Visible light driven photocatalytic degradation efficiency of both 1D and 3D CdS in the removal of erioglaucine are identical. Surprisingly, with 5 min of sonication, the highly crystalline 3D CdS stacked with many thin nanowires containing numerous active surface sites exhibited four-fold enhanced photodegradation efficiency in comparison to 1D and 2D CdS. Scavenger studies revealed that electrons and superoxide radicals are primary reactive species involved in the photodegradation of erioglaucine, while cyclic photodegradation studies revealed the good stability of 3D CdS against photocorrosion. Further, the photocatalytic hydrogen evolution studies also revealed the excellent activity of 3D CdS in comparison to 1D and 2D CdS. Thus, we find that the morphology indeed influences the photocatalytic activity. These results reveal that 3D CdS nanostructures investigated in the present work are efficient photocatalysts that could be fine-tuned for both environmental remediation and hydrogen generation applications. © 2019 Elsevier B.V.Item Bismuth oxybromide nanoplates embedded on activated charcoal as effective visible light driven photocatalyst(Elsevier B.V., 2020) Shenoy, S.; Sridharan, K.Nanostructured bismuth oxybromide (BiOBr) are one among the most significantly researched visible light driven photocatalyst, but their low specific surface area hinders higher rate of photodegradation. Herein, a single-step solution based synthesis technique is adopted to embed BiOBr on very little quantities of activated charcoal (AC), thereby improving its specific surface area and visible light absorption range. Nanoplate morphology of BiOBr and their embedment on AC are confirmed from electron microscopy. Interestingly, the embedment of BiOBr on just 0.5 wt% of AC (BiOBr-AC0.5) significantly enhanced the rate of salicylic acid photodegradation, which was six-fold higher than that of pristine BiOBr. © 2020 Elsevier B.V.Item 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 Graphitic C3N4/CdS composite photocatalyst: Synthesis, characterization and photodegradation of methylene blue under visible light(Elsevier B.V., 2020) Shenoy, S.; Tarafder, K.; Sridharan, K.Design and development of heterojunction photocatalysts is one among the main strategies for improving the photocatalytic activity of semiconductor materials. Here, we report the synthesis of a heterojunction photocatalyst by the embedment of cadmium sulphide (CdS) nanoparticles on the surface of graphitic carbon nitride (g-C3N4) layers through hydrothermal approach. The g-C3N4/CdS heterojunction photocatalyst exhibited two-fold and three-fold enhancement in the photodegradation efficiency in comparison to pristine CdS and g-C3N4, respectively in the removal of 20 ppm methylene blue dye molecules under visible light irradiation. The enhanced photocatalytic activity can be attributed to the formation of heterojunction and the synergistic effect of g-C3N4 and CdS in the promotion of charge separation and charge mobility that was tracked through photoluminescence spectroscopy. © 2020 Elsevier B.V.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