Boosted Charge Transfer via Coordinate Bond Construction in Porphyrin Metal–Organic Framework/ZnIn₂S₄ Core–Shell Heterostructures

Abstract

Intimate interface design at the molecular level in heterojunctions deserves significant attention since the charge transfer efficiency at the interfaces can greatly affect the catalytic performance. Herein, an efficient interface engineering strategy was reported to design a titanium porphyrin metal−organic framework−ZnIn 2 S 4 (TMF−ZIS) core−shell heterojunction which is tightly connected via coordination bonds (−N−Zn−). Such interfacial chemical bonds as the directional carrier transfer channels afforded improved charge separation efficiency compared to the physical composite of TMF and ZIS without chemical bonding. As a result, the optimized TMF−ZIS composite showed a 13.37 mmol•g −1 •h −1 H 2 production which is 47.7, 3.3, and 2.4 times that of TMF, ZIS, and mechanical mixing samples, respectively. Moreover, the composite also exhibited high photocatalytic tetracycline hydrochloride (TCH) degradation efficiency. Profiting from the core−shell structures, the ZIS shell efficiently prevented the aggregation and photocorrosion of TMF core particles which afforded enhanced chemical stability. Such an interface engineering strategy will be a versatile method to obtain highly effective organic−inorganic heterojunctions and offer new ideas for modulating the interfaces in the heterojunctions at the molecular level.

Improving the Photoactivity of Porphyrin-Based Metal–Organic Frameworks via Constructing [Ce–O] Active Site and Vacancy

“…The signals at 1322 and 1550 cm –1 were detected in the TCPP sample assigned to the A g and B 1g vibrational modes, respectively. Generally, the A g mode is generated by the stretching vibration of the porphyrin ring while the B 1g mode is generated from the pyrrole half-ring symmetric stretching modes . All of the peaks for TCPP can be seen in the CMF, CMF-X, and CMF­(Zn) samples, confirming the coordination of Ce ions with TCPP or TCPP (M).…”

Photothermal‐Enhanced S‐Scheme Heterojunction of Hollow Core–Shell FeNi2S4@ZnIn2S4 toward Photocatalytic Hydrogen Evolution

“…It is obviously that the photocurrent density for the hollow core–shell FNS@ZIS‐6 S‐scheme heterojunction is superior to ZIS and FNS, revealing an evident promotion in the restraint of the photogenerated electron–hole pairs recombination. [ 61,62 ]…”

Zr-based metal–organic framework PCN-222@defective ZnIn2S4 core–shell Z-scheme heterojunctions toward efficient charge separation and optimized photocatalytic performance

“…34–36 Various Z-scheme heterostructures based on the semiconductor and MOF have been confirmed for their significance with good visible-light response owing to the synergistic effect in the fields of photocatalysis, sensors and energy harvesting. 37,38…”