Tunable Band Engineering Management on Perovskite MAPbBr₃/COFs Nano‐Heterostructures for Efficient S–S Coupling Reactions

Abstract

Efficient artificial photosynthesis of disulfide bonds holds promises to facilitate reverse decoding of genetic codes and deciphering the secrets of protein multilevel folding, as well as the development of life science and advanced functional materials. However, the incumbent synthesis strategies encounter separation challenges arising from leaving groups in the ─S─S─ coupling reaction. In this study, according to the reaction mechanism of free‐radical‐triggered ─S─S─ coupling, light‐driven heterojunction functional photocatalysts are tailored and constructed, enabling them to efficiently generate free radicals and trigger the coupling reaction. Specifically, perovskites and covalent organic frameworks (COFs) are screened out as target materials due to their superior light‐harvesting and photoelectronic properties, as well as flexible and tunable band structure. The in situ assembled Z‐scheme heterojunction MAPB‐M‐COF (MAPbBr3 = MAPB, MA+ = CH3NH2+) demonstrates a perfect trade‐off between quantum efficiency and redox chemical potential via band engineering management. The MAPB‐M‐COF achieves a 100% ─S─S─ coupling yield with a record photoquantum efficiency of 11.50% and outstanding cycling stability, rivaling all the incumbent similar reaction systems. It highlights the effectiveness and superiority of application‐oriented band engineering management in designing efficient multifunctional photocatalysts. This study demonstrates a concept‐to‐proof research methodology for the development of various integrated heterojunction semiconductors for light‐driven chemical reaction and energy conversion.

Construction of MoS2/CdS heterojunction catalysts with crystal plane modulation for photocatalytic coupling of benzylamines under aerobic and anaerobic conditions

“…The heterojunction structure can not only inhibit the recombination of photogenerated carriers, but also stabilize the material. 12,13 In a traditional type II heterojunction, while the efficient separation of photogenerated electrons and holes is achieved, the redox ability of the semiconductor is inevitably weakened. 14,15 In recent years, Z-scheme heterojunctions have attracted extensive attention due to their ability to enhance the separation efficiency of photogenerated carriers, while also retaining the strong redox capability of semiconductors.…”

The construction of a MAPbBr3/La2Ti2O7 organic–inorganic dual perovskite heterojunction for photocatalytic CO2 reduction

“…4,11,12 Organic-inorganic hybrid perovskites, such as MAPbBr 3 , have been regarded as an ideal candidate for photocatalytic energy conversion reactions due to their long diffusion length, tunable band structure, and large light absorption coefficient. 2,3,[13][14][15][16][17] Unfortunately, the poor separation efficiency and serious recombination of the photo-excited charge carriers in MAPbBr 3 greatly limited their applications, which could be overcome by the construction of a heterostructure with two or more semiconductors with different band structures and lattice constants. 13,15 Consequently, a series of MAPbBr 3 -based heterostructures, such as MAPbBr 3 -g-C 3 N 4 , MAPbBr 3 -MXene, and MAPbBr 3 -COFs, for photocatalytic degradation and water splitting were proposed.…”

“…2,3,[13][14][15][16][17] Unfortunately, the poor separation efficiency and serious recombination of the photo-excited charge carriers in MAPbBr 3 greatly limited their applications, which could be overcome by the construction of a heterostructure with two or more semiconductors with different band structures and lattice constants. 13,15 Consequently, a series of MAPbBr 3 -based heterostructures, such as MAPbBr 3 -g-C 3 N 4 , MAPbBr 3 -MXene, and MAPbBr 3 -COFs, for photocatalytic degradation and water splitting were proposed. 3,13,15,16,18 The lattice mismatch between MAPbBr 3 and other semiconductors would bring about a defect, which would become the capture center and deteriorate the separation and transport efficiency of the charge carriers.…”

“…13,15 Consequently, a series of MAPbBr 3 -based heterostructures, such as MAPbBr 3 -g-C 3 N 4 , MAPbBr 3 -MXene, and MAPbBr 3 -COFs, for photocatalytic degradation and water splitting were proposed. 3,13,15,16,18 The lattice mismatch between MAPbBr 3 and other semiconductors would bring about a defect, which would become the capture center and deteriorate the separation and transport efficiency of the charge carriers. 19 Consequently, the design and synthesis of a MAPbBr 3 -based dual perovskite heterojunction simultaneously possessing the high separation efficiency of charge carriers and low level of lattice mismatch are of special importance for the efficient photocatalytic reaction.…”

“…S4, ESI †). To further illustrate the origin of the CO and CH 4 products, an isotope tracking experiment using 13 CO 2 as carbon resource was carried out (Fig. S5a, ESI †).…”