Reaction Mechanism and Selectivity Tuning of Propene Oxidation at the Electrochemical Interface.

Electrochemical conversion of propene is a promising technique for manufacturing commodity chemicals by using renewable electricity. To achieve this goal, we still need to develop high-performance electrocatalysts for propene electrooxidation, which highly relies on understanding the reaction mechanism at the molecular level. Although the propene oxidation mechanism has been well investigated at the solid/gas interface under thermocatalytic conditions, it still remains elusive at the solid/liquid interface under an electrochemical environment. Here, we report the mechanistic studies of propene electrooxidation on PdO/C and Pd/C catalysts, considering that the Pd-based catalyst is one of the most promising electrocatalytic systems. By electrochemical in situ attenuated total reflection Fourier transform infrared spectroscopy, a distinct reaction pathway was observed compared with conventional thermocatalysis, emphasizing that propene can be dehydrogenated at a potential higher than 0.80 V, and strongly adsorb via µ-C═CHCH3 and µ3-η2-C═CHCH3 configuration on PdO and Pd, respectively. The µ-C═CHCH3 is via bridge bonds on adjacent Pd and O atoms on PdO, and it can be further oxidized by directly taking surface oxygen from PdO, verified by the H218O isotope-edited experiment. A high surface oxygen content on PdO/C results in a 3 times higher turnover frequency than that on Pd/C for converting propene into propene glycol. This finding highlights the different reaction pathways under an electrochemical environment, which sheds light on designing next-generation electrocatalysts for propene electrooxidation.

Nanoscale hetero-interfaces for electrocatalytic and photocatalytic water splitting.

As green and sustainable methods to produce hydrogen energy, photocatalytic and electrochemical water splitting have been widely studied. In order to find efficient photocatalysts and electrocatalysts, materials with various composition, size, and surface/interface are investigated. In recent years, constructing suitable nanoscale hetero-interfaces can not only overcome the disadvantages of the single-phase material, but also possibly provide new functionalities. In this review, we systematically introduce the fundamental understanding and experimental progress in nanoscale hetero-interface engineering to design and fabricate photocatalytic and electrocatalytic materials for water splitting. The basic principles of photo-/electro-catalytic water splitting and the fundamentals of nanoscale hetero-interfaces are briefly introduced. The intrinsic behaviors of nanoscale hetero-interfaces on electrocatalysts and photocatalysts are summarized, which are the electronic structure modulation, space charge separation, charge/electron/mass transfer, support effect, defect effect, and synergistic effect. By highlighting the main characteristics of hetero-interfaces, the main roles of hetero-interfaces for electrocatalytic and photocatalytic water splitting are discussed, including excellent electronic structure, efficient charge separation, lower reaction energy barriers, faster charge/electron/mass transfer, more active sites, higher conductivity, and higher stability on hetero-interfaces. Following above analysis, the developments of electrocatalysts and photocatalysts with hetero-structures are systematically reviewed.

One-Pot Synthesis of Nitrogen-Doped TiO2 with Supported Copper Nanocrystalline for Photocatalytic Environment Purification under Household White LED Lamp.

Developing efficient and cheap photocatalysts that are sensitive to indoor light is promising for the practical application of photocatalysis technology. Here, N-doped TiO2 photocatalyst with loaded Cu crystalline cocatalyst is synthesized by a simple one-pot method. The structure is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy analysis, which exhibit that Cu metal nanocrystalline is uniformly deposited on the surface of N-doped TiO2 material. UV-Vis absorption spectra illustrate that the modified samples possess favorable visible light absorption properties and suppressed-electron hole separation. The as-fabricated Cu-loaded N-TiO2 materials show high activity in photocatalytic decomposing isopropanol and inactivating E.coliunder the irradiation of a household white LED lamp. The developed synthetic strategy and photocatalytic materials reported here are promising for indoor environment purification.

M1 Macrophage-Biomimetic Targeted Nanoparticles Containing Oxygen Self-Supplied Enzyme for Enhancing the Chemotherapy.

Tumor hypoxia is considered one of the key causes of the ineffectiveness of various strategies for cancer treatment, and the non-specific effects of chemotherapy drugs on tumor treatment often lead to systemic toxicity. Thus, we designed M1 macrophage-biomimetic-targeted nanoparticles (DOX/CAT@PLGA-M1) which contain oxygen self-supplied enzyme (catalase, CAT) and chemo-therapeutic drug (doxorubicin, DOX). The particle size of DOX/CAT@PLGA-M1 was 202.32 ± 2.27 nm (PDI < 0.3). DOX/CAT@PLGA-M1 exhibited a characteristic core-shell bilayer membrane structure. The CAT activity of DOX/CAT@PLGA-M1 was 1000 (U/mL), which indicated that the formation of NPs did not significantly affect its enzymatic activity. And in vitro drug release showed that the cumulative release rate of DOX/CAT@PLGA-M1 was enhanced from 26.93% to 50.10% in the release medium of hydrogen peroxide, which was attributed to the reaction of CAT in the NPs. DOX/CAT@PLGA-M1 displayed a significantly higher uptake in 4T1 cells, because VCAM-1 in tumor cells interacted with specific integrin (α4 and ß1), and thereby achieved tumor sites. And the tumor volume of the DOX/CAT@PLGA-M1 group was significantly reduced (0.22 cm3), which further proved the active targeting effect of the M1 macrophage membrane. Above all, a novel multifunctional nano-therapy was developed which improved tumor hypoxia and obtained tumor targeting activity.

Stabilizing CuGaS2 by crystalline CdS through an interfacial Z-scheme charge transfer for enhanced photocatalytic CO2 reduction under visible light.

CuGaS2 is one of the most excellent visible-light-active photocatalysts for CO2 reduction and water splitting. However, CuGaS2 suffers from serious deactivation in photocatalytic reactions, which is mainly due to the photo-oxidation induced self-corrosion (Cu+ to Cu2+). Here, we constructed a CuGaS2/CdS hybrid photocatalyst dominated by a Z-scheme charge transfer mechanism. The transfer of photo-generated electrons from excited nanocrystalline CdS to CuGaS2 across the coherent interface reduces Cu2+ formation and favors Cu+ regeneration. This process suppresses the deactivation of CuGaS2 and maintains high performance. Both the activity and stability of photocatalytic CO2 reduction to produce CO over the CuGaS2/CdS hybrid were remarkably improved, which was approximately 4-fold higher than CuGaS2 and 3-fold higher than CdS in converting CO2 into CO. Our study demonstrates that even using the semiconductors prone to photo-corrosion, it is possible to obtain satisfactory catalytic activity and stability by designing efficient Z-scheme-charge-transfer-type photocatalysts.