DOI: 10.1002/asia.202100262
Full Paper
Photocatalytic Hydrogen Evolution Coupled with Production of
Highly Value-Added Organic Chemicals by a Composite
Photocatalyst CdIn S @MIL-53-SO Ni
2
4
3
[a]
Huan-Huan Zhang, Guo-Peng Zhan, Zi-Kun Liu, and Chuan-De Wu*
Abstract: Photocatalytic water splitting coupled with the
production of highly value-added organic chemicals is of
significant importance, which represents a very promising
pathway for transforming green solar energy into chemical
superior photocatalytic properties of the composite photo-
catalyst CdIn S @MIL-53-SO Ni should be ascribed to coat-
2
4
3
1/2
ing suspended ion catalyst (SIC), consisting of redox-active
II
Ni ions in the anionic pores of coordination network MIL-53-
À
energy. Herein, we report
a
composite photocatalyst
SO , on the surface of photoactive CdIn S , which endows
3
2 4
CdIn S @MIL-53-SO Ni1/2, which is highly efficient on prompt-
photogenerated electron-hole pairs separate more efficiently
2
4
3
ing water splitting for the production of H in the reduction
for high rate production of H and selective production of
2
2
half-reaction and selective oxidation of organic molecules for
the production of highly value-added organic chemicals in
the oxidation half-reaction under visible light irradiation. The
highly value-added organic products, demonstrating great
potential for practical applications.
Introduction
electronic, electronic and optical properties, has been used in
solar cells, photoconductors, optical devices and photocatalysis
by effectively inhibiting the recombination of photogenerated
Attributed to the unique feature of harvesting free solar energy
under green conditions, photocatalysis has been extensively
studied in numerous fields, including water splitting, carbon
dioxide reduction, molecular synthesis, pollutant degrada-
tion and metal reduction. Because H is an ideal intermediate
in green energy cycle, photocatalytic synthesis of H by splitting
water is of significant importance.
positive Gibbs free energy (ΔG =237.1 kJmol ) of the reaction
[14]
electron-hole pairs. Compared with In S and CdS individuals,
2
3
[
1]
[15]
CIS exhibits superior performances in photocatalysis. How-
ever, the photogenerated electrons and holes are easily
recombined if there is no suitable co-catalytically redox-active
[2]
[3]
[4,5]
2
[16]
site on the surface of photocatalyst CIS. Photocorrosion was
*
2
[
6,7]
II
However, the highly
often occurred because S species is easily oxidized by OH
θ
À 1
[17]
species to form CdSO4.
To improve the photocatalytic
would result in back-reaction that could heavily deteriorate the
photocatalytic efficiency for overall water splitting. Consider-
performance and stability, cocatalysts were often employed as
the hole and electron traps by inhibiting their recombination,
lowering the intrinsic energy barriers and suppressing the
[8]
ing that the production of O is insignificant, sacrificial agents
2
[18,19]
(e.g. triethylamine, triethanolamine, ethanol and methanol)
photo-corrosion.
There are many noble-metals (e.g. Pt, Ru
were usually used as electron donors to improve the H
and Pd) and transition-metals (e.g. Co, Ni and Fe) that have
been introduced into the photocatalytic system as redox-active
2
[9,10]
evolution efficiency.
It is unfortunate that the high toxicity
[20,21]
and cost of sacrificial agents heavily frustrated the practical
application of this technology. A promising approach to solve
this issue is to produce highly value-added organic chemicals
by the photocatalytic oxidation half-reaction, when producing
H2 product in the reduction half-reaction. Even though the
oxidation half-reaction has been used to oxidize organic
chemicals in photocatalysis, excessive dosages resulted in low
sites to improve the photocatalytic efficiency.
Even though
in situ photodeposition has been one of the most convenient
pathways to load cocatalyst sites, the in situ produced redox-
active metallic species is easily re-oxidized upon exposed in air
and easily leached off during photocatalysis, leading to
deactivate the photocatalysts and/or contaminate the reaction
[22–24]
mixtures.
[11–13]
substrate conversion and product selectivity.
We have demonstrated that suspended ion catalysts (SICs)
could effectively prevent leaching of metallic species and
endow ionic redox-active sites freely mobile by confining ionic
redox-active sites in the ionic pores of metal-organic frame-
works (MOFs), which exhibited highly catalytic efficiency and
The ternary chalcogenide, cadmium indium sulphide
CdIn S , abbreviated as CIS), demonstrating outstanding opto-
(
2
4
[
a] H.-H. Zhang, G.-P. Zhan, Z.-K. Liu, Prof. Dr. C.-D. Wu
Key Laboratory of Excited-State Materials of Zhejiang Province
and State Key Laboratory of Silicon Materials
Department of Chemistry
stability in heterogeneous catalysis, electrocatalysis and
[25–27]
photocatalysis.
To improve the photocatalytic efficiency
Zhejiang University
Hangzhou, 310027 (P. R. China)
E-mail: cdwu@zju.edu.cn
and stability of the ternary chalcogenide photocatalyst CIS, we
coated SIC MIL-53-SO Ni , consisting of suspended redox-
3
1/2
II
À
active Ni ions inside the anionic pores of MOF MIL-53-SO , on
3
collection on Supramolecular Catalysis and Catalyst Immobilization.
the surface of CIS, which resulted a composite photocatalyst
CIS@MIL-53-SO Ni1/2, demonstrating high photocatalytic effi-
3
Chem Asian J. 2021, 16, 1–9
1
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