Dendritic boron and nitrogen doped high-entropy alloy porous carbon fibers for high-efficiency hydrogen evolution reaction.

Among various electrocatalysts, high-entropy alloys (HEAs) have gained significant attention for their unique properties and excellent catalytic activity in the hydrogen evolution reaction (HER). However, the precise synthesis of HEA catalysts in small sizes remains challenging, which limits further improvement in their catalytic performance. In this study, boron- and nitrogen-doped HEA porous carbon nanofibers (HE-BN/PCNF) with an in situ-grown dendritic structure were successfully prepared, inspired by the germination and growth of tree branches. Furthermore, the dendritic fibers constrained the growth of HEA particles, leading to the synthesis of quantum dot-sized (1.67 nm) HEA particles, which also provide a pathway for designing HEA quantum dots in the future. This work provides design ideas and guiding suggestions for the preparation of borated HEA fibers with different elemental combinations and for the application of dendritic nanofibers in various fields.

Rationally designing of Co-WS2 catalysts with optimized electronic structure to enhance hydrogen evolution reaction.

Designing and developing cost-effective, high-performance catalysts for hydrogen evolution reaction (HER) is crucial for advancing hydrogen production technology. Tungsten-based sulfides (WSx) exhibit great potential as efficient HER catalysts, however, the activity is limited by the larger energy required for water dissociation under alkaline conditions. Herein, we adopt a top-down strategy to construct heterostructure Co-WS2 nanofiber catalysts. The experimental results and theoretical simulations unveil that the work functions-induced built-in electric field at the interface of Co-WS2 catalysts facilitates the electron transfer from Co to WS2, significantly reducing water dissociation energy and optimizing the Gibbs free energy of the entire reaction step for HER. Besides, the self-supported catalysts of Co-WS2 nanoparticles confining 1D nanofibers exhibit an increased number of active sites. As expected, the heterostructure Co-WS2 catalysts exhibit remarkable HER activity with an overpotential of 113 mV to reach 10 mA cm-2 and stability with 30 h catalyzing at 23 mA cm-2. This work can provide an avenue for designing highly efficient catalysts applicable to the field of energy storage and conversion.

Oxygen Vacancy-Enhanced Centrosymmetric Breaking of SrFeO3- x for Piezoelectric-Catalyzed Synthesis of H2O2.

Normally, only noncentrosymmetric structure of the materials can potentially be piezoelectric. Thus, it is limited in the field of piezoelectricity for the centrosymmetric structure of the material. In this work, the performance of piezoelectricity is successfully achieved from centrosymmetric SrFeO3- x by modulating oxygen vacancies, which have a surface piezoelectric potential up to 93 mV by using Kelvin-probe force microscopy (KPFM). Moreover, the piezoelectric effects of SrFeO3- x are also evaluated by piezoelectric catalytic effect and density functional theory calculations (DFT). The results show that the piezo-catalytic degradation of tetracycline reaches 96% after 75 min by ultrasonic mechanical vibration and the production of H2O2 by SrFeO3- x piezoelectric synthesis could reach 1821 µmol L-1. In addition, the DFT results indicate that the intrinsic effect of oxygen vacancies effectively promotes the adsorption and activation of O2 and H2O as well as intermediates and improves the piezoelectric catalytic activity. This work provides an effective basis for realizing the piezoelectricity of centrosymmetric materials and regulating the development of piezoelectric catalytic properties.

Constructing CoO/Mo2 C Heterostructures with Interfacial Electron Redistribution Induced by Work Functions for Boosting Overall Water Splitting.

Space charge transfer of heterostructures driven by the work-function-induced built-in field can regulate the electronic structure of catalysts and boost the catalytic activity. Herein, an epitaxial heterojunction catalyst of CoO/Mo2 C with interfacial electron redistribution induced by work functions (WFs) is constructed for overall water splitting via a novel top-down strategy. Theoretical simulations and experimental results unveil that the WFs-induced built-in field facilitates the electron transfer from CoO to Mo2 C through the formed "Co─C─Mo" bond at the interface of CoO/Mo2 C, achieving interfacial electron redistribution, further optimizing the Gibbs free energy of primitive reaction step and then accelerating kinetics of hydrogen evolution reaction (HER). As expected, the CoO/Mo2 C with interfacial effects exhibits excellent HER catalytic activity with only needing the overpotential of 107 mV to achieve 10 mA cm-2 and stability for a 60-h continuous catalyzing. Besides, the assembled CoO/Mo2 C behaves the outstanding performance toward overall water splitting (1.58 V for 10 mA cm-2 ). This work provides a novel possibility of designing materials based on interfacial effects arising from the built-in field for application in other fields.

Synergistic Effects of Magnetic Z-Scheme g-C3N4/CoFe2O4 Nanofibres with Controllable Morphology on Photocatalytic Activity.

The rational design of interfacial contacts plays a decisive role in improving interfacial carrier transfer and separation in heterojunction photocatalysts. In Z-scheme photocatalysts, the recombination of photogenerated electron-hole pairs is prevented so that the redox capacity is maintained. Here, one-dimensional graphitic carbon nitride (g-C3N4)/CoFe2O4 fibres were synthesised as a new type of magnetic Z-scheme visible-light photocatalyst. Compared with pure g-C3N4 and CoFe2O4, the prepared composite photocatalysts showed considerably improved performance for the photooxidative degradation of tetracycline and methylene blue. In particular, the photodegradation efficiency of the g-C3N4/CoFe2O4 fibres for methylene blue was approximately two and seven times those of g-C3N4 and CoFe2O4, respectively. The formation mechanism of the Z-scheme heterojunctions in the g-C3N4/CoFe2O4 fibres was investigated using photocurrent spectroscopy and electrochemical impedance spectroscopy. We proposed that one of the reasons for the improved photodegradation performance is that the charge transport path in one-dimensional materials enables efficient photoelectron and hole transfer. Furthermore, the internal electric field of the prepared Z-scheme photocatalyst enhanced visible-light absorption, which provided a barrier for photoelectron-hole pair recombination.

Flexible PTh/GQDs/TiO2 composite with superior visible-light photocatalytic properties for rapid degradation pollutants.

Flexible fiber membranes for pollutant removal have received increasing attention due to their high adsorption performance and easy recycling characteristics. However, due to the lack of environmentally friendly regeneration, some adsorption membranes have low regeneration efficiency, especially in terms of chemical adsorption, so they lack reusability. This study prepares a series of conducting polymer [PAn (polyaniline) or PPy (polypyrrole) or PTh (polythiophene)] graphene quantum dots (GQDs, the size of GQDs is about 20 nm)/TiO2 ternary fiber membranes via a facile electrospinning method with chemical deposition. Remarkably, this creates an anatase TiO2 and π-conjugated system. The combination is beneficial to the photocatalytic degradation of organic pollutants, showing synergistic promotion in both the degradation rate and the degree of decomposition. The UV-vis test shows that the combination of GQDs broadens the optical response threshold of TiO2, from near ultraviolet region excitation to visible region excitation. At the same time, the conductive polymer load further reduces the energy required for photogenerated electron transfer, which theoretically improves the degradation effect. Photocatalytic degradation tests showed that the PTh/GQDs/TiO2 fiber membrane exhibited significant high photocatalytic activity of visible-light in the methylene blue (MB) and TC degradation. The degradation rate level is 92.90% and 80.58%, respectively and the MB removal is more than 4 times that of bare TiO2 membrane. After photocatalytic regeneration four times, the regeneration efficiency can be maintained above 95%. Notably, various experimental results show that the interface charge transfer mechanism between GQDs/TiO2 and PTh follows the Z-scheme heterojunction, which maximizes the retention of strong reducing electrons and oxidation holes. In the degradation, the active species of ·O2 - and ·OH, make different contributions in the photocatalysts, which oxidize and break down the pollutant molecules into small molecules and then to harmless substances. According to the electronegativity difference of the material itself, PTh acts as electron acceptor in the degradation system, and TiO2 fiber membrane doped with GQDs acts as electron donor. The present research, not only offers feasibility of the PTh/GQDs/TiO2 flexible fiber membrane as an environment-friendly catalyst, but also motivates researchers to develop flexible fiber materials for future photocatalytic technology.