Designing and developing visible-light-responsive materials for solar to chemical energy is an efficient and promising approach to green and sustainable carbon-neutral energy systems. Herein, a facile in situ growth hydrothermal strategy using Mo-modified ZnIn 2 S 4 (Mo-ZIS) nanosheets coupled with NiTiO 3 (NTO) microrods to synthesize multifunctional Mo-modified ZIS wrapped NTO microrods (Mo-ZIS@NTO) photocatalyst with enhanced interfacial electric field (IEF) effect and typical S-scheme heterojunction is reported. Mo-ZIS@NTO catalyst possesses wide-spectrum light absorption properties, excellent visible light-to-thermal energy effect, electron mobility, charges transfer, and strong IEF and exhibits excellent solar-to-chemical energy conversion for efficient visible-light-driven photocatalytic hydrogen evolution. Notably, the engineered Mo 1.4 -ZIS@NTO catalyst exhibits superior performance with H 2 evolution rate of up to 14.06 mmol g −1 h − 1 and the apparent quantum efficiency of 44.1% at 420 nm. The scientific explorations provide an in-depth understanding of microstructure, S-scheme heterojunction, enhanced IEF, Mo-dopant facilitation effect. Moreover, the theoretical simulations verify the critical role of Mo element in promoting the adsorption and activation of H 2 O molecules, modulating the H adsorption behavior on active S sites, and thus accelerating the overall catalytic efficiency. The photocatalytic hydrogen evolution mechanism via S-scheme heterojunction with adjustable IEF regulation over Mo 1.4 -ZIS@NTO is also demonstrated.

Photocatalytic water splitting to produce hydrogen is considered to be a promising approach to clean, sustainable, and renewable energy. The highly efficient photocatalysts play a key role in photocatalytic hydrogen production. Owing to its high charge carrier mobility and tunable band gap, black phosphorus (BP) has emerged as a potential photocatalyst. However, when using BP for photocatalytic hydrogen production individually, the inherent instability and light-harvesting capability greatly restricted the further application, as well as the fast photogenerated electron–hole recombination. Herein, a novel heterostructured photocatalyst BP-MoO3–x was prepared via the direct ball-milling method for H2 photogeneration. The result demonstrated that coupling BP with the localized surface plasmonic defective MoO3–x through covalent Mo–P bond improves the chemical stability, enables the visible-to-near infrared photons to harvest, and promotes the photogenerated carrier separation. As a result, the BP-MoO3–x could deliver high photocatalytic hydrogen production rates of 396.3 and 156.4 μmol·g–1·h–1 under visible and near-infrared lights, which are ∼40 and 80 times higher than that of BP without any sacrificial agent, respectively. Furthermore, the BP-MoO3–x also shows good stability under visible light irradiation from cycle stability testing. Combining with density functional theory (DFT) calculations, the synergistic effect of Z-scheme BP-MoO3–x heterostructure and strong localized surface plasmon resonance (LSPR) enhances light-harvesting capacity and improves the photoexcited charge transfer efficiency.

Surface patterning of in situ pore formation was studied in this research based on the solvent treatment breath figure (stBF) method. By applying the volatile solvent onto the preshaped polymeric objects under humid conditions, hexagonally arranged pore arrays were formed on the surface efficiently. The stBF method was performed on many different polymeric samples with planar and nonplanar surfaces, and facile pore formation was achieved on these surfaces by conducting the solvent treatment in different ways of dipping, casting, and vapor treatment. The water droplets condensed from the humid air were proved to be the origin of the pore arrays just like the case of classic BF process. The influencing factors including solvent types, surfactant addition, and polymer types were evaluated for their impact on the resultant stBF morphologies. In situ threedimensional (3D) pore formation was achieved for both macroscopic-and microscopic-sized 3D-structured objects. Chemical patterning of the introduced minor component was also achieved in the stBF pore-forming process with high efficiency and site selectivity. Moreover, the capability of pore formation and erasure with high spatial accuracy using multiple solvent treatments was revealed for the stBF method to make rewritable and hierarchical patterns. Both the selective chemical decoration and rewritable patterning serve as intriguing features of the stBF method. The establishment of the stBF method makes the classic BF process more flexible to practice and less dependent on the external conditions, showing potential for applications such as facile surface patterning with multifunctionality on devices with complex geometry.

ABSTRACT“Inverse emulsion”‐“breath figures” (Ie‐BF) method was introduced for fabricating porous films with protein arrays decorating the interior of the obtained polymeric pores. Compared with the traditional BF method in which only hydrophobic or amphiphilic components could be used, Ie‐BF method created a system with water phase carrying water‐soluble protein before solution casting, which makes it possible to obtain patterned protein arrays within the BF structure in one‐step. The stability of the inverse emulsion system is an intractable problem solved by high shearing emulsification. Experimental parameters, including the concentration of the matrix polymer, water/oil ratio of the IE, amount of both emulsifier and protein in IE, were evaluated for establishing an optimal condition to prepare fine BF arrays by following the Ie‐BF method. Proteins tagged with fluorescein isothiocyanate were added into the emulsion to cast films, and pores efficiently enriched by proteins were revealed by the images of fluorescence microscope, indicating the successful preparation of protein arrays. Among all the approaches of establishing patterned structures of biomacromolecules, Ie‐BF shows promising potential in future applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47084.

A facile method to fabricate honeycomb‐patterned biocompatible polycaprolactone (PCL) films with cavities that are selectively decorated with protein by one‐step method is developed in this study. To carry out this method, proteins carried in water are dispersed into chloroform solution of PCL to form inverse emulsion with the assistance of the chitosan particles serving as emulsifier. The evaporation of the organic solvent in the inverse emulsion on substrate under a high‐humidity atmosphere leads to the formation of ordered porous arrays incorporated with proteins on the inner surface of the cavities. The method, based on the combination of breath figures and inverse emulsion template, provides a reliable route for the directed assembly of water‐soluble materials into patterned polymer matrix. It has the potential to be further established as a novel procedure to fabricate a multifunctional hybrid porous structure containing hydrophilic component based on the breath figure method.