Construction of a Bi2S3/Bi0.5Na0.5TiO3 Composite Catalyst with S Vacancies for Efficient Piezo-Photocatalytic Hydrogen Production.

Photocatalytic hydrogen production with low environmental and economic costs is expected to be a powerful means to alleviate energy and environmental problems. However, how to inhibit the rapid recombination of photogenerated carriers is a challenge that photocatalytic hydrogen production has to face. In this study, the coupling of the piezoelectric effect and vacancy engineering into the photocatalytic reaction process synergistically promoted carrier separation, thereby promoting the improvement of hydrogen production performance. Specifically, the novel dual piezoelectric Bi2S3/Bi0.5Na0.5TiO3 (BS-12/BNT) piezo-photocatalyst rich in S vacancies was synthesized by an impregnation method. The hydrogen generation rate of 5% BS-12/BNT under the combined impact of light and ultrasound was up to 1019.39 µmol/g/h, which is 9.5 times higher than that of pure BNT. Various characterization analyses have confirmed that the piezoelectric-photocatalytic activity of BS/BNT composite materials is significantly improved, mainly due to the introduction of S vacancies and piezoelectric fields, which enhance the absorption of sunlight, reduce interface resistance, and so raise the photogenerated carriers' separation efficiency. In addition, the stability of BS/BNT is significantly better than that of the previously synthesized catalysts. Finally, according to the results of XPS, UV-vis, and ESR, the active groups and possible electron transfer paths generated during the piezoelectric-photocatalytic hydrogen production process were studied. This work presents a new approach to promote hydrogen production performance through the synergistic effect of the piezoelectric effect and S vacancies.

Piezoelectric Polarization and Sulfur Vacancy Enhanced Photocatalytic Hydrogen Evolution Performance of Bi2S3/ZnSn(OH)6 Piezo-photocatalyst.

The combination of piezoelectric catalysis and photocatalysis could effectively enhance the carrier separation efficiency and further improve the hydrogen production activity. However, piezoelectric polarization always suffers from a low polarization strength, which severely restricts its actual applications. In this study, we successfully synthesized a novel sulfur vacancy-rich Bi2S3/ZnSn (OH)6 (BS-12/ZSH) piezo-photocatalyst for hydrogen evolution through water splitting. Notably, the piezo-photocatalytic hydrogen generation rate of the 8% BS-12/ZSH catalyst (336.21 µmol/g/h) was superior to that of pristine ZSH (29.71 µmol/g/h) and BS-12 (21.66 µmol/g/h). In addition, the hydrogen generation for 8% BS-12/ZSH (336.21 µmol/g/h) under ultrasonic coupling illumination was significantly higher than that under single illumination (52.09 µmol/g/h) and ultrasound (121.90 µmol/g/h), owing to the cooperative interaction of the sulfur vacancy and piezoelectric field. Various characterization analyses confirmed that (1) the introduction of sulfur vacancies in BS-12 provided more active sites, (2) BS-12 with sulfur vacancies acted as a co-catalyst to accelerate the hydrogen production rate, and (3) the piezoelectric field eliminated the electrostatic shielding and offered an additional driving force, which effectively promoted the separation of electron-hole pairs. This research clearly reveals the synergistic effect between piezocatalysis and photocatalysis as well as offers a promising sight for the rational design of high-efficiency piezo-photocatalysts.

RuSe2/CeO2heterostructure as a novel electrocatalyst for highly efficient alkaline hydrogen evolution.

Constructing heterojunction to adjust the electronic structure of catalysts is a promising strategy for synergistically improving electrocatalytic activity. In addition, RuSe2is recognized as an effective alternative to Pt for boosting alkaline hydrogen evolution reaction (HER) on account of its outstanding catalytic properties. Herein, novel RuSe2/CeO2heterojunction electrocatalysts are fabricated through hydrothermal and thermal treatment methods. The optimal 50% RuSe2/CeO2heterojunction electrocatalyst exhibits a low HER overpotential of 16 mV to attain 10 mA cm-2current density and Tafel slope of 66.1 mV dec-1for hydrogen evolution in 1.0 M KOH. At the same time, the 50% RuSe2/CeO2heterojunction electrocatalyst also maintains a stable HER activity for 50 h or 3000 CV cycles. The experimental results show that formation of heterogeneous interface between RuSe2and CeO2results in the redistribution of electrons at the RuSe2/CeO2interface, thereby changing the electronic structure of RuSe2and enhancing the performance of the RuSe2/CeO2electrocatalyst. This work may provide a feasible way to design efficient hydrogen evolution heterojunction electrocatalysts by modulating the electronic structure in alkaline electrolytes.

Spindle Nanorods of CeO2 and NiS Heterointerface Coated by the NC Layer: A High-Performance Bifunctional Electrocatalyst for Water Splitting.

Currently, nickel sulfides are widely employed in the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), thanks to the narrow electronegativity difference of only 0.67 eV between nickel and sulfur. Among them, NiS stands out in terms of the OER performance; however, its HER performance and stability remain somewhat inadequate. The construction of heterogeneous interfaces can efficiently improve the HER performance and regulate the electronic structure of the NiS catalyst. CeO2 has been discovered to possess exceptional electronic modulation capabilities, which may lead to the effective enhancement of both HER and OER of the NiS catalyst. As a result, a nitrogen-doped carbon-coated CeO2-NiS heterogeneous interface catalyst (NC/NiS-CeO2) is designed as a bifunctional electrocatalyst for HER and OER with high performance. The NC/NiS-CeO2 catalyst demonstrates excellent HER (47 mV at 10 mA cm-2) and OER (92 mV at 10 mA cm-2) performances in a 1 M KOH alkaline solution. Characterization analysis reveals that the coupling of the heterostructure interface, which consists of CeO2 and NiS, significantly enhances electron conduction, the synergistic effect, and the electrocatalytic activity of the electrode. This study demonstrates that the HER and OER activity can be effectively improved by constructing a rational heterogeneous interface.

RuSe2-CoTe Heterogeneous Surfaces Coated with NC Layer for Excellent HER Performance under Alkaline Condition.

Electrocatalytic hydrogen production has been a promising high-purity hydrogen production technology, attracting a large number of researchers' research interest. Ru has a hydrogen binding capacity similar to Pt, but its price is far lower than Pt, making it a promising alternative to Pt. However, a single Se electronic structure modulation is not sufficient to enable RuSe2 to be used for practical applications on a large scale due to the lack of electrons. Therefore, choosing a suitable way to electronically modulate the Ru atoms in RuSe2 can effectively improve the activity of the catalyst. Cobalt telluride (CoTe) can significantly enhance electrocatalytic performance due to tellurium's low electronegativity and excellent metal properties. In this work, the NC layer possesses excellent electrical conductivity and CoTe acts as an electron donor to optimize the electronic structure locally and trigger electron transfer efficiently. The RuSe2-CoTe/NC electrode requires an overpotential of only 25.4 mV (10 mA cm-2), which is superior to that of RuSe2/NF (65 mV) and CoTe/NC (115 mV). Meanwhile, the Tafel slope of RuSe2-CoTe/NC (67.8 mV dec-1) was better than that of RuSe2/NF (113.6 mV dec-1) and CoTe/NC (209.5 mV dec-1), showing that the build-up of the superior heterojunction makes the RuSe2-CoTe/NC with better hydrogen evolution reaction (HER) reaction kinetics. In addition, after 30 h of long-term stability testing, no significant decrease in catalytic activity was observed, proving the good stability of the RuSe2-CoTe/NC catalyst.

Fabrication of multiphase MoSe2 modified BiOCl nanosheets for efficient piezo-photoelectric hydrogen evolution and antibiotic degradation.

Efficient spatial charge separation plays a crucial role in improving the photocatalytic performance. Therefore, 1T/2H MoSe2/BiOCl (1T/2H MS/BOC) and 2H MoSe2/BiOCl (2H MS/BOC) piezo-photocatalysts are synthesized. By combining piezoelectric catalysis and photocatalysis, a highly active piezo-photocatalytic process is realized. The optimal 1T/2H MS/BOC piezo-photocatalyst displays superior diclofenac (DCF) degradation and hydrogen (H2) evolution activity under the combined action of ultrasound and light. In particular, the DCF degradation kinetic constant (k) of optimal 0.5% 1T/2H MS/BOC under the synergistic effect of ultrasound and light is 0.057 min-1, which is 8.1 and 6.3 times higher than those of BiOCl (0.007 min-1) and 0.5% 2H MS/BOC (0.009 min-1). Moreover, the H2 evolution rate of 0.5% 1T/2H MS/BOC is 122.5 µmol g-1 h-1, which is also higher than those of BiOCl (45.8 µmol g-1 h-1) and 2H MS/BOC (49.5 µmol g-1 h-1). The dramatic improvement in the DCF degradation and H2 evolution piezo-photocatalytic performance of 1T/2H MS/BOC catalysts is ascribed to the built-in polarization electric field and abundance of active sites of 1T/2H MS/BOC as well as the advantageous band structure between BiOCl and 1T/2H MoSe2. Additionally, three probable degradation pathways of DCF were put forward from the results of liquid chromatography-mass spectrometry (LCMS) and density functional theory (DFT) calculations. This study provides the design strategy of high efficiency piezo-photocatalysts in environmental purification and energy-generation fields based on phase and band structure engineering.

Tentacle-like core-shell CoNi2S4/C3N4 bifunctional electrocatalysts for efficient overall alkaline water splitting.

Stable and efficient bifunctional electrocatalysts are of great significance for sustainable energy conversion and human society sustainability. However, conventional electrocatalytic materials tend to exhibit high overpotentials and unsatisfactory chemical activities. Herein, we construct novel CoNi2S4/C3N4 nanowires on a nickel foam (NF) electrode as a bifunctional electrocatalyst for alkaline water splitting by a two-step hydrothermal and thermal annealing process. The prepared CoNi2S4/C3N4 electrocatalyst exhibits superior HER (e.g. 40 mV (ηH210)) and OER (e.g. 110 mV (ηO210)) activities in a 1 M KOH electrolyte, which are much smaller than those of bare NF, Co@NF, NiCoO@NF and most reported materials. Furthermore, the stability test at 10 mA cm-2 for 20 h for the CoNi2S4/C3N4 electrocatalyst shows no obvious decay and proves the excellent stability of CoNi2S4/C3N4. In this work, the unique tentacle-like CoNi2S4/C3N4 nanowire nanostructure leads to minimized interfacial resistance and abundant channels during electrocatalysis. Moreover, comprehensive analysis results show that Ni(Co)OOH active sites, which are beneficial for excellent OER activity, partially form on the surface of CoNi2S4/C3N4 during electrocatalysis. Finally, the CoNi2S4/C3N4∥CoNi2S4/C3N4 two-electrode system is constructed and it exhibits a low-voltage water splitting capability of 1.40 V.

Z-Scheme CdIn2S4/Bi2WO6 Heterojunction for High Piezo-Photo Synergetic Performance.

The piezoelectric effect triggered by mechanical energy could establish an internal electric field to effectively modulate the separation behavior of carriers. Herein, a novel CdIn2S4/Bi2WO6 (CIS/BWO) piezo-photocatalyst for removing diclofenac (DCF) from water was constructed for the first time. Encouragingly, the photocatalytic degradation activity of CIS/BWO was effectively promoted through the piezoelectric effect. Specifically, 10% CIS/BWO exhibited promising DCF degradation performance under co-excitation of light irradiation and ultrasonic vibration, with a degradation efficiency of 99.9% within 40 min, much higher than that of pure photocatalysts (72.3%) and piezocatalysts (60.3%). Meanwhile, an in-depth study of the charge carrier separation mechanism of the CIS/BWO composite under the piezo-photo synergy condition was proposed. Both the built-in electric field induced by the piezoelectric effect in BWO and the Z-scheme transfer path of the CIS/BWO heterojunction are beneficial to interfacial charge transfer. Moreover, the Z-scheme mechanism was further demonstrated by trapping experiments and the electron spin resonance (ESR) technique. Finally, the corresponding intermediates of DCF over CIS/BWO composites and possible degradation pathways were also investigated by DFT calculations and liquid chromatography-mass spectrometry.

Efficient Charge Separation via MoSe2 Nanosheets with Tunable 1T Phase Contents: Piezoreduction of Cr(VI) to Cr(III) and Piezodegradation of RhB.

Piezocatalysis is a promising technology to address environmental pollution by converting mechanical energy into chemical energy. Herein, MoSe2 nanosheets with different 1T phase percentages (ranging from 30 to 80%) were constructed by adjusting hydrothermal temperature. Moreover, the roles of phase engineering in the piezocatalysis were thoroughly investigated by degrading rhodamine B and reducing Cr(VI) in ultrasonic vibration conditions. In particular, MoSe2 prepared at 220 °C (MoSe2-220) exhibits ultrahigh observed constant kobs and degradation rate k, which is superior to most reported catalysts to date. The experimental results indicate that the introduction of the 1T phase increases the active sites of the material, improves the conductivity, and inhibits the recombination of electrons and holes. Moreover, an internal electric field in the 2H phase induced by piezoelectric polarization is facilitated to separate electron-hole pairs, enabling the degradation and reduction to proceed. The capture experiments and EPR tests further confirm that •O2- and •OH are main reactive species, and a rational mechanism is finally put forward. This study offers a clear understanding of phase engineering in piezocatalysis and provides an efficiency strategy to construct highly efficient piezocatalysts.

Removal of toxic indigo blue with integrated biomaterials of sodium carboxymethyl cellulose and chitosan.

Sodium carboxymethyl cellulose (NaCMC) and chitosan (CS) are successfully combined via amidation, and the obtained product, CMC-CS-A, is used for the adsorption of toxic indigo blue (IB) for the first time. The results of control experiments indicate that the adsorption performance of CMC-CS-A is superior to that of NaCMC, CS, and the composites of NaCMC and CS integrated via electrostatic attractions (CMC-CS-E), which can be attributed to the unique interconnected porous network structure of the as-prepared CMC-CS-A. The mass fraction of CS in the CMC-CS-A is also investigated to achieve the best adsorption of IB, and it reveals that satisfactory removal of IB can be achieved at the CMC-CS-A (50wt%). Important parameters such as contact time, temperature and initial concentration are discussed in detail in this work. Finally, adsorption isotherms and adsorption kinetics are investigated and compared by using classic models, and the results indicate that the adsorption fits well with the Langmuir isotherm model and the pseudo-second-order kinetic model. It opens a new avenue for the effective and convenient treatment of textile wastewater with integrated natural biopolymers.

Enhanced bioconversion of ethylene glycol to glycolic acid by a newly isolated Burkholderia sp. EG13.

Burkholderia sp. EG13 with high ethylene glycol-oxidizing activity was isolated from soil, which could be used for the synthesis of glycolic acid from the oxidation of ethylene glycol. Using the resting cells of Burkholderia sp. EG13 as biocatalysts, the optimum reaction temperature and pH were 30 °C and 6.0, respectively. After 24 h of biotransformation, the yield of glycolic acid from 200 mM ethylene glycol was 98.8 %. Furthermore, an integrated bioprocess for the production of glycolic acid which involved in situ product removal (ISPR) was investigated. Using fed-batch method with ISPR, a total of 793 mM glycolic acid has been accumulated in the reaction mixture after the 4th feed.