TY - JOUR

T1 - Octahedral Tantalum Bromide Clusters as Catalysts for Light-Driven Hydrogen Evolution

AU - Hernández, Jhon Sebastián

AU - Guevara, Daniela

AU - Shamshurin, Maxim

AU - Benassi, Enrico

AU - Sokolov, Maxim N

AU - Feliz, Marta

N1 - This research was funded by project PID2021−123163OB-I00 funded by MCIN/AEI/10.13039/501100011033/ and FEDER A way of making Europe and Severo Ochoa center of excellence program (CEX2021−001230-S). J.S.H. gratefully acknowledges to Programa Santiago Grisolía (Consejo Superior de Investigaciones Científicas and Generalitat Valenciana; grant number GRISOLIA/2021/054). Funding for open access charge: CRUE-Universitat Politècnica de València. Computationalresources were kindly provided by Laboratory of complex compounds synthesis (Nikolaev Institute of Inorganic Chemistry SB RAS).

PY - 2023/11/20

Y1 - 2023/11/20

N2 - The development of an efficient hydrogen generation strategy from aqueous protons using sunlight is a current challenge aimed at the production of low-cost, easily accessible, renewable molecular hydrogen. For achieving this goal, non-noble metal containing and highly active catalysts for the hydrogen evolution reaction (HER) are desirable. Octahedral tantalum halide clusters {Ta6(μ-X)12}2+ (X = halogen) represent an emerging class of such HER photocatalysts. In this work, the photocatalytic properties of octahedral aqua tantalum bromide clusters toward HER and in acid and homogeneous aqueous conditions were investigated. The [{Ta6Bri12}Bra2(H2O)a4]·4H2O (i = inner ligand; a = apical ligand) compound is revealed to be an efficient precatalyst in acid (HBr) conditions and with methanol as the sacrificial agent. A response surface methodology (RSM) study was applied for the optimization of the HER conditions, considering the concentrations of both additives (methanol and HBr) as independent variables. An optimal H2 production of 11 mmol·g-1 (TON = 25) was achieved, which displays exceptional catalytic properties compared to regular Ta-based materials. The aqua tantalum bromide clusters assist in the photocatalytic hydrogen generation in agreement with energy-conversion schemes, and plausible active catalytic species and a reaction mechanism were proposed from computational and experimental perspectives.

AB - The development of an efficient hydrogen generation strategy from aqueous protons using sunlight is a current challenge aimed at the production of low-cost, easily accessible, renewable molecular hydrogen. For achieving this goal, non-noble metal containing and highly active catalysts for the hydrogen evolution reaction (HER) are desirable. Octahedral tantalum halide clusters {Ta6(μ-X)12}2+ (X = halogen) represent an emerging class of such HER photocatalysts. In this work, the photocatalytic properties of octahedral aqua tantalum bromide clusters toward HER and in acid and homogeneous aqueous conditions were investigated. The [{Ta6Bri12}Bra2(H2O)a4]·4H2O (i = inner ligand; a = apical ligand) compound is revealed to be an efficient precatalyst in acid (HBr) conditions and with methanol as the sacrificial agent. A response surface methodology (RSM) study was applied for the optimization of the HER conditions, considering the concentrations of both additives (methanol and HBr) as independent variables. An optimal H2 production of 11 mmol·g-1 (TON = 25) was achieved, which displays exceptional catalytic properties compared to regular Ta-based materials. The aqua tantalum bromide clusters assist in the photocatalytic hydrogen generation in agreement with energy-conversion schemes, and plausible active catalytic species and a reaction mechanism were proposed from computational and experimental perspectives.

UR - https://www.mendeley.com/catalogue/1c42327f-3578-3a99-81fd-ec539cd2af94/

U2 - 10.1021/acs.inorgchem.3c03045

DO - 10.1021/acs.inorgchem.3c03045

M3 - Article

C2 - 37935006

VL - 62

SP - 19060

EP - 19069

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 46

ER -