A metal-organic cage incorporating multiple light harvesting and catalytic centres for photochemical hydrogen production.
Photocatalytic water splitting is a natural but challenging chemical way of harnessing renewable solar power to generate clean hydrogen energy. Here we report a potential hydrogen-evolving photochemical molecular device based on a self-assembled ruthenium-palladium heterometallic coordination cage, incorporating multiple photo- and catalytic metal centres. The photophysical properties are investigated by absorption/emission spectroscopy, electrochemical measurements and preliminary DFT calculations and the stepwise electron transfer processes from ruthenium-photocentres to catalytic palladium-centres is probed by ultrafast transient absorption spectroscopy. The photocatalytic hydrogen production assessments reveal an initial reaction rate of 380 μmol h-1and a turnover number of 635 after 48 h. The efficient hydrogen production may derive from the directional electron transfers through multiple channels owing to proper organization of the photo- and catalytic multi-units within the octahedral cage, which may open a new door to design photochemical molecular devices with well-organized metallosupramolecules for homogenous photocatalytic applications.
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Sha
S
Chen
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Kang
K
Li
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Fang
F
Zhao
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Lei
L
Zhang
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Mei
M
Pan
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Yan-Zhong
YZ
Fan
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Jing
J
Guo
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Jianying
J
Shi
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.|State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
Cheng-Yong
0000-0003-3604-7858
CY
Su