02816nas a2200241 4500008004100000022001400041245014600055210006900201260000800270300001400278490000700292520194900299100002302248700001502271700002102286700002902307700001802336700002402354700001802378700001902396700003002415856012902445 2025 eng d a2050-748800aMultifunctional NiO/Ti3+-TiO2 for concurrent water reduction and glycerol oxidation to value added products by sunlight driven photocatalysis0 aMultifunctional NiOTi3TiO2 for concurrent water reduction and gl cJAN a2105-21200 v133 a

The present work describes the synthesis of bifunctional-mesoporous-self-doped Ti3+ containing NiO/TiO2 photocatalysts for concurrent utilization of e- and h+ to produce H2 and value-added products (VAPs), respectively, from aqueous glycerol. UV-vis diffuse reflectance results and band gap analysis revealed an improved light absorption due to integration of Ni2+ with Ti3+/TiO2. Various electrochemical, PL and TRPL spectral analyses demonstrate p-n heterojunction formation between NiO and Ti3+-TiO2, which enhances charge separation and helps in achieving improved activity. HRTEM analysis of NiO/Ti3+-TiO2 nanocomposites revealed that NiO is highly dispersed on TiO2 with interfacial heterojunctions between them. XPS results demonstrate the partial reduction of Ti4+ to Ti3+ and Ni-Ti synergetic interaction in NiO/TiO2 to form NiO/Ti3+-TiO2 nanocomposites. EXAFS studies show that the Ni-O bond distance is similar to that of NiTiO3 suggesting electronic integration of components of the photocatalyst by forming a Ni2+-O-Ti3+/Ti4+ lattice network. Ni2+/Ti3+-TiO2 nanocomposites as a bifunctional photocatalyst exhibited significantly enhanced activity in H2 production and conversion of glycerol to VAPs, namely, glycolaldehyde, 1,3-dihydroxyacetone, and formic acid; formation of these products highlights not only oxidation, but also C-C cleavage of glycerol. The NiO/Ti3+-TiO2 photocatalysts fabricated in thin film form displayed higher photocatalytic efficiency than their powder counterpart. Among NiO/Ti3+-TiO2 nanocomposites NiT-3 exhibits the highest H2 yield at 15.62 mmol h-1 g-1, which is 38 times higher than that of bare TiO2. The enhanced photocatalytic activity is ascribed to the high charge carrier density, the synergistic interaction between Ni2+ and Ti3+-TiO2, formation of a p-n heterojunction at the interface between NiO and Ti3+-TiO2 and effective utilization of charge carriers for redox reactions.

1 aRajendran, Sivaraj1 aSaju, Simi1 aMani, Sunesh, S.1 aAsoka, Anantha, Krishnan1 aSaha, Arindam1 aArun, Pushkaran, S.1 aGhosh, Biplab1 aMathew, Thomas1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/multifunctional-nioti3-tio2-concurrent-water-reduction-and-glycerol-oxidation-value-added19043nas a2200229 45000080041000002450148000412100071001892600008002603000014002684900007002825201819000289100002318479700001518502700002118517700002918538700001818567700002418585700001818609700001918627700003018646856013718676 2025 eng d00aMultifunctional NiO/Ti3+–TiO2 for concurrent water reduction and glycerol oxidation to value added products by sunlight driven photocatalysis0 aMultifunctional NiOTi3–TiO2 for concurrent water reduction and g cJAN a2105-21200 v133 a

The present work describes the synthesis of bifunctional-mesoporous-self-doped Ti3+ containing NiO/TiO2 photocatalysts for concurrent utilization of e and h+ to produce H2 and value-added products (VAPs), respectively, from aqueous glycerol. UV-vis diffuse reflectance results and band gap analysis revealed an improved light absorption due to integration of Ni2+ with Ti3+/TiO2. Various electrochemical, PL and TRPL spectral analyses demonstrate p–n heterojunction formation between NiO and Ti3+–TiO2, which enhances charge separation and helps in achieving improved activity. HRTEM analysis of NiO/Ti3+–TiO2 nanocomposites revealed that NiO is highly dispersed on TiO2 with interfacial heterojunctions between them. XPS results demonstrate the partial reduction of Ti4+ to Ti3+ and Ni–Ti synergetic interaction in NiO/TiO2 to form NiO/Ti3+–TiO2 nanocomposites. EXAFS studies show that the Ni–O bond distance is similar to that of NiTiO3 suggesting electronic integration of components of the photocatalyst by forming a Ni2+–O–Ti3+/Ti4+ lattice network. Ni2+/Ti3+–TiO2 nanocomposites as a bifunctional photocatalyst exhibited significantly enhanced activity in H2 production and conversion of glycerol to VAPs, namely, glycolaldehyde, 1,3-dihydroxyacetone, and formic acid; formation of these products highlights not only oxidation, but also C–C cleavage of glycerol. The NiO/Ti3+–TiO2 photocatalysts fabricated in thin film form displayed higher photocatalytic efficiency than their powder counterpart. Among NiO/Ti3+–TiO2 nanocomposites NiT-3 exhibits the highest H2 yield at 15.62 mmol h−1 g−1, which is 38 times higher than that of bare TiO2. The enhanced photocatalytic activity is ascribed to the high charge carrier density, the synergistic interaction between Ni2+ and Ti3+–TiO2, formation of a p–n heterojunction at the interface between NiO and Ti3+–TiO2 and effective utilization of charge carriers for redox reactions.

1 aRajendran, Sivaraj1 aSaju, Simi1 aMani, Sunesh, S.1 aAsoka, Anantha, Krishnan1 aSaha, Arindam1 aArun, Pushkaran, S.1 aGhosh, Biplab1 aMathew, Thomas1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/multifunctional-nioti3%E2%80%93tio2-concurrent-water-reduction-and-glycerol-oxidation-value-added