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제125회 대한화학회 학술발표회 및 총회 Earth Abundant Molecular HX-Splitting Photocatalysts for Solar Energy Storage

등록일
2020년 2월 6일 14시 49분 40초
접수번호
0927
발표코드
INOR1-1 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
화 10시 : 40분
발표형식
심포지엄
발표분야
Inorganic Chemistry - Emerging Researchers in Inorganic Chemistry
저자 및
공동저자
SeungJun Hwang
Department of Chemistry , Pohang University of Science and Technology, Korea
Photochemical splitting of hydrohalic acids (HX) into their elemental constituents H2 and X2 (2 HX -> H2 + X2) represents a chemical approach to solar-to-fuels energy conversion. To this end, this thesis has been directed towards developing new chemical platforms that manage both of the requisite two-electron half-reactions of HX splitting: proton reduction and halide oxidation. In previous work in the field, the halide oxidation half cycle remains the kinetic bottleneck of a HX photocycle and chemical traps are required to promote halogen extrusion. This heavily mitigates the utility of the photocatalysis for energy storing applications. In addition, heretofore, little progress has been made toward energy storing halogen elimination chemistry with earth-abundant 3d metal complexes because of their short excited state lifetimes. High-yielding, endothermic Cl2 photoelimination chemistry from mononuclear Ni(III) complexes have been developed utilizing a new strategy based on secondary coordination sphere effects to suppress undesired rapid back reaction. Building upon the success of our previous photocrystallography experiments, we have applied steady-state photocrystallography techniques to the NiX3 complexes. Steady-state photocrystallography of Ni complex shows substantial elongation of apical Ni–Br(1) bond from 2.464(2) Å in the ground state to 3.70(4) Å in the photoinduced structure whereas the two basal Ni–Br bonds are crystallographically unchanged (2.3615(7) Å (dark), and 2.35(5) Å (photoinduced)) showing that the apical halide that is extruded in the photoelimination process.

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