[NiBr(SeO_(2)Br)(bipy)2](1),[NiBr(SeO_(2)Br)(phen)_(2)](2),and[NiCl(SeO_(2)Cl)(bipy)_(2)](3),represent the first nickel complexes incorporating dioxo-haloselenate anions.These complexes were selected due to their uniq...[NiBr(SeO_(2)Br)(bipy)2](1),[NiBr(SeO_(2)Br)(phen)_(2)](2),and[NiCl(SeO_(2)Cl)(bipy)_(2)](3),represent the first nickel complexes incorporating dioxo-haloselenate anions.These complexes were selected due to their unique structural features,and light absorption properties,which make them promising candidates for photocatalytic applications.The compounds were immobilized onto mesoporous TiO_(2)(m-TiO_(2)),resulting in photocatalysts 1@m-TiO_(2),2@m-TiO_(2),and 3@m-TiO_(2),which were evaluated for solar-driven water splitting to produce hydrogen.Electrochemical analyses revealed suitable HOMO–LUMO energy levels for visible-light activation,and X-ray photoelectron spectroscopy confirmed changes in surface composition upon immobilization.Among the photocatalysts,2@m-TiO_(2)exhibited the highest H_(2)production,achieving 927μmol g^(−1)in 6 hours,outperforming both 1@m-TiO_(2)(803μmol g^(−1))and 3@m-TiO_(2)(810μmol g^(−1)),as well as reference materials m-TiO_(2)and Degussa P25.Moreover,complex 1 demonstrated intrinsic electrochemical activity for H_(2)evolution in acidic media.Recycling experiments showed the stability of 2@m-TiO_(2)over three cycles,confirming its robustness.These findings not only demonstrate the effective cocatalytic role of complexes 1–3 in enhancing H_(2)generation but also shed light on interfacial photoinduced processes via HOMO–LUMO evaluation and XPS analysis.This study introduces the first example of nickel-based dioxo-haloselenate complexes as cocatalysts,opening new avenues for the development of sustainable hydrogen-evolving materials.展开更多
基金supported by funding from Fundação de AmparoàPesquisa do Estado do Rio Grande do Sul-FAPERGS-(Programa Pesquisador Gaúcho-PqG-21/2551-0002123-3)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior(CAPES/PrInt 88881.310412/2018-01)Finance Code 001,Conselho Nacional de Desenvolvimento Científico e Tecnológico-CNPq(Universal-405965/2023)+1 种基金FINEP.C.A.B.is gratefully to Conselho Nacional de Desenvolvimento Científico e Tecnológico-CNPq(141046/2021-0)for the scholarshipthe assistance of the Core Facility BioSupraMol supported by the DFG and to LNNano for the XPS analyses(proposal 20240473).
文摘[NiBr(SeO_(2)Br)(bipy)2](1),[NiBr(SeO_(2)Br)(phen)_(2)](2),and[NiCl(SeO_(2)Cl)(bipy)_(2)](3),represent the first nickel complexes incorporating dioxo-haloselenate anions.These complexes were selected due to their unique structural features,and light absorption properties,which make them promising candidates for photocatalytic applications.The compounds were immobilized onto mesoporous TiO_(2)(m-TiO_(2)),resulting in photocatalysts 1@m-TiO_(2),2@m-TiO_(2),and 3@m-TiO_(2),which were evaluated for solar-driven water splitting to produce hydrogen.Electrochemical analyses revealed suitable HOMO–LUMO energy levels for visible-light activation,and X-ray photoelectron spectroscopy confirmed changes in surface composition upon immobilization.Among the photocatalysts,2@m-TiO_(2)exhibited the highest H_(2)production,achieving 927μmol g^(−1)in 6 hours,outperforming both 1@m-TiO_(2)(803μmol g^(−1))and 3@m-TiO_(2)(810μmol g^(−1)),as well as reference materials m-TiO_(2)and Degussa P25.Moreover,complex 1 demonstrated intrinsic electrochemical activity for H_(2)evolution in acidic media.Recycling experiments showed the stability of 2@m-TiO_(2)over three cycles,confirming its robustness.These findings not only demonstrate the effective cocatalytic role of complexes 1–3 in enhancing H_(2)generation but also shed light on interfacial photoinduced processes via HOMO–LUMO evaluation and XPS analysis.This study introduces the first example of nickel-based dioxo-haloselenate complexes as cocatalysts,opening new avenues for the development of sustainable hydrogen-evolving materials.
