Enhanced activation of peroxymonosulfate with cobalt-doped manganese-iron oxides for contaminant degradation: Regulation of oxygen vacancy defects.

Peroxymonosulfate (PMS) based on heterogeneous catalytic reaction was a promising advanced oxidation process (AOP) to remove refractory contaminants. However, the contaminant degradation efficiency was challenged by the limited number of catalytic active site and low capacity for durable electron transfer. In this study, cobalt-doped manganese-iron oxides (CoxMn1-xFe2O4) rich in oxygen vacancy (Ov) were synthesized using a microwaved hydrothermal method and applied to activate PMS for bisphenol A (BPA) degradation, which achieved the complete removal of BPA within 30 min. In all samples, Co0.5Mn0.5Fe2O4 exhibited good catalytic activity for PMS, which was approximately 21.10 times higher than that of MnFe2O4. The results of density functional theory calculations and in-situ characterization demonstrated that the enhanced performance was ascribed to the generation of Ov and the enrichment of active site, which significantly accelerated the cycling of redox pairs and improved the PMS adsorption, which was more favorable to the formation of active specie in the electron transport process. The oxidation process involved both free radical and non-radical mechanisms, with main reactive species of O2-, and 1O2 being responsible for BPA degradation. In addition, the effects of different aqueous matrices, the results of reusability experiments, and ecotoxicity assessment experiments demonstrated the viability of the Co0.5Mn0.5Fe2O4/PMS system for real sewage purification. This research revealed a structural regulation method to enhance the catalytic activity of the material and offered new perspectives on the engineering of rich Ov.

Promoting effect of Cu as electron transfer medium on NH3-SCO reaction in asymmetric Ag-Ov-Ti-Sm-Cu ring active site.

Selective catalytic oxidation of ammonia (NH3-SCO) has become an effective method to reduce ammonia (NH3) emissions, and is a key part to solve the problem of NH3 pollution. Nevertheless, the optimization of this technology's performance relies heavily on innovation and the development of catalyst design. In this study, a SmCuAgTiOx catalyst with an asymmetric Ag-Ov-Ti-Sm-Cu ring active site was prepared and applied to the NH3-SCO reaction. The low conversion of Cu-based catalysts in NH3 at low temperature and the inherent low N2 selectivity of Ag-based catalysts were solved. The successful creation of the asymmetric ring active site improved the catalyst's reduction performance. Additionally, Cu, acting as an electron transfer medium, plays a crucial role in enhancing electron transfer within the asymmetric ring active site, thus increasing the redox cycle of the catalyst during the reaction. In addition, some lattice oxygen is lost in the catalyst, resulting in the formation of a large number of oxygen vacancies. This process stimulates the adsorption and activation of surface-adsorbed oxygen, facilitating the conversion of NH3 to an amide (NH2) intermediate during the reaction and reducing non-selective oxidation. The N2 selectivity was improved without significantly affecting the performance of Ag-based catalyst. In-situ diffuse reflectance fourier transform infrared spectroscopy (In-situ DRIFTS) analysis reveals that the SmCuAgTiOx catalyst primarily follows an "internal" selective catalytic reduction (iSCR) mechanism in the NH3-SCO reaction, complemented by the imide mechanism. The asymmetric Ag-Ov-Ti-Sm-Cu ring active site developed in this study provides a new perspective for efficiently solving NH3 pollution in the future.

Integrating carbon quantum dots with oxygen vacancy modified nickel-based metal organic frameworks for photocatalytic CO2 reduction to CH4 with approximately 100 % selectivity.

Solar-light-driven reduction of CO2 into renewable fuels has great potential in the production of sustainable energy, addressing the energy crisis and environmental problems simultaneously. However, it is a significant challenge to achieve high selectivity for the conversion of CO2 into CH4, which is a type of fuel with a high calorific value. Herein, carbon quantum dots (CQDs) were integrated with an oxygen vacancy modified nickel-based metal organic frameworks (NiMOFs) to form the CQDs-X/NiMOFV series, which exhibited superior performance for CO2 photoreduction into CH4 compared with pure NiMOFs in the presence of hole scavengers under visible light irradiation. The highest yielding rate of CH4 (1 mmol g-1 h-1) and selectivity (97.58 %) were obtained using a CQDs-25/NiMOFV catalyst. Most importantly, in diluted CO2 atmosphere, the yield of CH4 was almost unchanged and the selectivity of CH4 over CQDs-25/NiMOFV was higher than that in pure CO2. The superior performance of CQDs-25/NiMOFV may be attributed to the following two factors: (i) both CQDs and oxygen vacancies facilitate the transmission of electrons to promote the eight-electron reaction producing CH4, and (ii) oxygen vacancies can act as the electron trap to capture the photogenerated electrons to react with adsorbed CO2 on Ni2+. This study offers a valuable strategy for designing efficient photocatalysts to convert CO2 into CH4 with superior selectivity.

In-situ construction of N-doped Zn0.6Cd0.4S/oxygen vacancy-rich WO3 Z-scheme heterojunction compound for boosting photocatalytic hydrogen production.

Photocatalytic water splitting technology for H2 production represents a promising and sustainable approach to clean energy generation. In this study, a high concentration of oxygen vacancies was introduced into tungsten trioxide (WO3) to create a vacancy-rich layer. This modified WO3 (WO3-x) was then combined with N-doped Zn0.6Cd0.4S through a hydrothermal synthesis, resulting in the formation of a Z-scheme heterojunction composite aimed at enhancing photocatalytic performance. Under visible light, the H2 production activity of the composite reached an impressive 8.52 mmol·g-1 without adding co-catalyst Pt. This corresponds to enhancements of 7.82 and 4.39 times the production yield of pure ZCS and ZCSN, respectively. However, the hydrogen production increased to 21.98 mmol·g-1 when Pt was added as a co-catalyst. Furthermore, an array of characterizations were employed to elucidate the presence of oxygen vacancies and the establishment of the Z-scheme heterojunction. This structural enhancement significantly facilitates the utilization of photo-generated electrons while effectively preventing photo-corrosion of ZCSN, thus improving material stability. Our study provides a new scheme for the incorporation of oxygen-rich vacancy and the construction of Z-scheme heterojunction, demonstrating a synergistic effect that greatly advances photocatalytic performance.

Assisting molybdenum trioxide catalysis by engineering oxygen vacancy for enhancing hydrogen storage performance of magnesium hydride.

Magnesium hydride (MgH2) as an ideal hydrogen storage carrier whose hydrogen storage performance can be effectively improved by transition metal-based catalysts. To construct highly active catalysts, much attention has been paid to the regulation of transition metal components while less attention has been paid to non-transition metal components especially oxygen, leading certain limitations. Herein, further improved hydrogen storage performance of MgH2 can be obtained by adjusting oxygen vacancy content in molybdenum trioxide (MoO3) catalyst. Specifically, compared with pure MgH2 (1.1 wt%) and MgH2-10 wt% MoO3 (4.5 wt%), more hydrogen (5.9 wt%) can be released by MgH2-10 wt% MoO3-x (MoO3 with abundant oxygen vacancies) at 300.0 °C within 499.0 s. Besides, superb capacity retention (6.1 wt%, 99.0 %) after 50 isothermal hydrogen ab/desorption cycles can be obtained for MgH2-10 wt% MoO3-x. Through rigorous comparative experiments and theoretical calculations, the excellent catalytic activity of MoO3-x is demonstrated to come from the abundant oxygen vacancies and the active substances (polyvalent Mo and nano-sized MgO) it assists to form during ball milling process. This work verifies the feasibility for further improving the catalytic activity of transition metal-based catalysts by tuning non-transition metal elements and thus provides a new strategy in catalyzed MgH2 system.

Oxygen vacancies enhancing hierarchical NiCo2S4@MnO2 electrode for flexible asymmetric supercapacitors.

The limited energy density of supercapacitors hampers their widespread application in electronic devices. Metal oxides, employed as electrode materials, suffer from low conductivity and stability, prompting extensive research in recent years to enhance their electrochemical properties. Among these efforts, the construction of core-shell heterostructures and the utilization of oxygen vacancy (VO) engineering have emerged as pivotal strategies for improving material stability and ion diffusion rates. Herein, core-shell composites comprising NiCo2S4 nanospheres and MnO2 nanosheets are grown in situ on carbon cloth (CC), forming nanoflower clusters while introducing VO defects through a chemical reduction method. Density functional theory (DFT) results proves that the existence of VO effectively enhances electronic and structural properties of MnO2, thereby enhancing capacitive properties. The electrochemical test results show that NiCo2S4@MnO2-V3 exhibits excellent 1376 F g-1 mass capacitance and 2.06 F cm-2 area capacitance at 1 A g-1. Moreover, NiCo2S4@MnO2-V3//activated carbon (AC) asymmetric supercapacitor (ASC) can achieve an energy density of 39.7 Wh kg-1 at a power density of 775 W kg-1, and maintains 15.5 Wh kg-1 even at 7749.77 W kg-1. Capacitance retention is 73.1 % after 10,000 cycles at 5 A g-1, and coulombic efficiency reaches 100 %, demonstrating satisfactory cycle stability. In addition, the device's excellent flexibility offers broad application prospects in wearable electronic applications.

Water adsorption on ferroelectric PbTiO3 (0 0 1) surface: A density functional theory study.

In this work, combining the density functional theory (DFT) calculations and the ab initio molecular dynamics (AIMD) simulations, the water adsorption behavior, including the molecular and the dissociative adsorption on the negatively polarized (0 0 1) surface of ferroelectric PbTiO3 was comprehensively studied. Our theoretical results show that the dissociative adsorption of water is more energetically favorable than the molecular adsorption on the pristine PbTiO3 (0 0 1) surface. It has been also found that introducing surface oxygen vacancies (OV) can enhance the thermodynamic stability of dissociative adsorption of water molecule. The AIMD simulations demonstrate that water molecule can spontaneously dissociate into hydrogen atoms (H) and hydroxyl groups (OH) on the pristine PbTiO3 (0 0 1) surface at room temperature. Moreover, the surface OV can effectively facilitate the dissociative adsorption of water molecules, leading to a high surface coverage of OH group, thus giving rise to a high reactivity for water splitting on defective PbTiO3 (0 0 1) surface with OV. Our results not only comprehensively understand the reason for the photocatalytic water oxidation activity of single domain PbTiO3, but also shed light on the development of high performance ferroelectric photocatalysts for water splitting.

BiOBr/FeMoO4 composite achieves oxygen vacancy concentration adjustment to promote persulfate activation degradation of organic pollutants in saline water.

The investigation about the mechanism of crystal plane regulation on the generation of oxygen vacancies remains a challenge. In this paper, BiOBr/FeMoO4 composites were synthesized by precise control of crystal plane growth, and it exhibited the enhanced concentration of oxygen vacancies due to lower formation energy of oxygen vacancies. The composite performs higher photo-Fenton-like ability for degrading oxytetracycline hydrochloride (OTC). Structural analyses and theoretical calculations reveal that crystal plane regulation induces significant changes in oxygen vacancy concentration. The BiOBr/FeMoO4/peroxydisulphate (PDS) /light system, which dominated by the non-radical pathway, degraded 96.8 % ± 1.0 % of OTC within 30 min. The activation mechanism of the system and the degradation pathway of OTC were elucidated. The intermediates in the degradation process of OTC were evaluated using liquid chromatograph-mass spectrometer (LC-MS), toxicity evaluation software tool (T.E.S.T) and soybean germination experiments. This work offers novel insights into the pivotal role of crystal plane directional regulation in the quantitative generation of oxygen vacancies.

Ti3+/Ti4+ and Co2+/Co3+ redox couples in Ce-doped Co-Ce/TiO2 for enhancing photothermocatalytic toluene oxidation.

Cerium and cobalt loaded Co-Ce/TiO2 catalyst prepared by impregnation method was investigated for photothermal catalytic toluene oxidation. Based on catalyst characterizations (XPS, EPR and H2-TPR), redox cycle between Co and TiO2 (Co2+ + Ti4+ ↔ Co3+ + Ti3+) results in the formation of Co3+, Ti3+ and oxygen vacancies, which play important roles in toluene catalytic oxidation reaction. The introduction of Ce brings in the dual redox cycles (Co2+ + Ti4+ ↔ Co3+ + Ti3+, Co2+ + Ce4+ ↔ Co3+ + Ce3+), further promoting the elevation of reaction sites amount. Under full spectrum irradiation with light intensity of 580 mW/cm2, Co-Ce/TiO2 catalyst achieved 96% of toluene conversion and 73% of CO2 yield, obviously higher than Co/P25 and Co/TiO2. Co-Ce/TiO2 efficiently maintains 10-hour stability test under water vapor conditions and exhibits better photothermal catalytic performance than counterparts under different wavelengths illumination. Photothermal catalytic reaction displays improved activities compared with thermal catalysis, which is attributed to the promotional effect of light including photocatalysis and light activation of reactive oxygen species.

Heteropoly blue-modified ultrathin bismuth oxychloride nanosheets with oxygen vacancies for efficient photocatalytic nitrogen fixation in pure water.

Photocatalytic nitrogen reduction is a promising green technology for ammonia synthesis under mild conditions. However, the poor charge transfer efficiency and weak N2 adsorption/activation capability severely hamper the ammonia production efficiency. In this work, heteropoly blue (r-PW12) nanoparticles are loaded on the surface of ultrathin bismuth oxychloride nanosheets with oxygen vacancies (BiOCl-OVs) by electrostatic self-assembly method, and a series of xr-PW12/BiOCl-OVs heterojunction composites have been prepared. Acting as a robust support, ultrathin two-dimensional (2D) structure of BiOCl-OVs inhibits the aggregation of r-PW12 nanoparticles, enhancing the interfacial contact between r-PW12 and BiOCl. More importantly, the existence of oxygen vacancies (OVs) provides abundant active sites for efficient N2 adsorption and activation. In combination of the enhanced light absorption and promoted photogenerated carriers separation of xr-PW12/BiOCl-OVs heterojunction, under simulated solar light, the optimal 7r-PW12/BiOCl-OVs exhibits an excellent photocatalytic N2 fixation rate of 33.53 µmol g-1h-1 in pure water, without the need of sacrificial agents and co-catalysts. The reaction dynamics is also monitored by in situ FT-IR spectroscopy, and an associative distal pathway is identified. Our study demonstrates that construction of heteropoly blues-based heterojunction is a promising strategy for developing high-performance N2 reduction photocatalysts. It is anticipated that combining of different defects with heteropoly blues of different structures might provide more possibilities for designing highly efficient photocatalysis systems.

Control interfacial charge transfer behavior by creating surface defects on structure unit of heterojunction to drive carrier separation for enhancing photocatalytic CO2 reduction.

Controlling interfacial charge transfer behavior of heterojunction is an arduous issue to efficiently drive separation of photogenerated carriers for improving the photocatalytic activity. Herein, the interface charge transfer behavior is effectively controlled by fabricating an unparalleled VO-NiWO4/PCN heterojunction that is prepared by encapsulating NiWO4 nanoparticles rich in surface oxygen vacancies (VO-NiWO4) in the mesoporous polymeric carbon nitride (PCN) nanosheets. Experimental and theoretical investigations show that, differing with the traditional p-n junction, the direction of built-in electric field between p-type NiWO4 and n-type PCN is reversed interestingly. The strongly codirectional built-in electric field is also produced between the surface defect region and inside of VO-NiWO4 besides in the space charge region, the dual drive effect of which forcefully propels interface charge transfer through triggering Z-Scheme mechanism, thus significantly improving the separation efficiency of photogenerated carriers. Moreover, the unique mesoporous encapsulation structure of VO-NiWO4/PCN heterostructure can not only afford the confinement effect to improve the reaction kinetics and specificity in the CO2 reduction to CO, but also significantly reduce mass transfer resistance of molecular diffusion towards the reaction sites. Therefore, the VO-NiWO4/PCN heterostructure demonstrates the preeminent activity, stability and reusability for photocatalytic CO2 reduction to CO reaction. The average evolution rate of CO over the optimal 10 %-VO-NiWO4/PCN composite reaches around 2.5 and 1.8 times higher than that of individual PCN and VO-NiWO4, respectively. This work contributes a fresh design approach of interface structure in the heterojunction to control charge transfer behaviors and thus improve the photocatalytic performance.

Synergistic regulation of d-band center photocatalytic hydrogen evolution at S-scheme heterojunction reduction sites through defect engineering and interface electric field.

The efficiency of photocatalytic hydrogen evolution can be significantly enhanced while maintaining cost-effectiveness through the synergistic effect of defect surface engineering and multi-component heterojunctions. The structure and properties of NiCo2O4 nanorods were modified by inducing oxygen vacancies at different temperatures in this study, resulting in improved optical properties and electron adsorption capacity. The presence of oxygen vacancies leads to a reduction in the band gap of NiCo2O4, thereby enhancing electron transport efficiency through band gap engineering. Simultaneously, surface properties undergo changes, and vacancy defects serve as electron trapping centers, facilitating an increased participation of electrons in the hydrogen evolution reaction process. The dodecahedron KMP with a cavity structure is additionally introduced to form an S-scheme heterojunction with NiCo2O4. This establishes a novel mechanism for electron transport, which effectively enhances the separation of electron-hole pairs and improves the redox capacity of the photocatalytic system. The adsorption of intermediates in the hydrogen production process is enhanced through synergistic regulation of d-band centers via surface defect engineering and S-scheme heterojunction. Additionally, this approach improves the separation efficiency of electron-hole pairs and accelerates electron transfer dynamics, significantly enhancing hydrogen production efficiency.

Synergistic engineering of heterostructure and oxygen vacancy in cobalt hydroxide/aluminum oxyhydroxide as bifunctional electrocatalysts for urea-assisted hydrogen production.

Designing inexpensive, high-efficiency and durable bifunctional catalysts for urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) is an encouraging tactic to produce hydrogen with reduced energy expenditure. Herein, oxygen vacancy-rich cobalt hydroxide/aluminum oxyhydroxide heterostructure on nickel foam (denoted as Co(OH)2/AlOOH/NF-100) has been fabricated using one step hydrothermal process. Theoretical calculation and experimental results indicate the electrons transfer from Co(OH)2 to highly active AlOOH results in the interfacial charge redistribution and optimization of electronic structure. Abundant oxygen vacancies in the heterostructure could improve the conductivity and simultaneously serve as the active sites for catalytic reaction. Consequently, the optimal Co(OH)2/AlOOH/NF-100 demonstrates excellent electrocatalytic performance for HER (62.9 mV@10 mA cm-2) and UOR (1.36 V@10 mA cm-2) due to the synergy between heterointerface and oxygen vacancies. Additionally, the in situ electrochemical impedance spectrum (EIS) for UOR suggests that the heterostructured catalyst exhibits rapid reaction kinetics, mass transfer and current response. Importantly, the urea-assisted electrolysis composed of the Co(OH)2/AlOOH/NF-100 manifests a low cell voltage (1.48 V @ 10 mA cm-2) in 1 M KOH containing 0.5 M urea. This work presents a promising avenue to the development of HER/UOR bifunctional electrocatalysts.

Molecular mechanisms of iron nanominerals formation in fungal extracellular polymeric substances (EPS) layers during fungus-mineral interactions.

Extracellular polymeric substances (EPS), which envelop on fungal hyphae surface, interact strongly with minerals and play a crucial role in the formation of nanoscale minerals during biomineralization in nature environments. However, it remains poorly understood about the molecular mechanisms of nanominerals (i.e., iron nanominerals) formation in fungal EPS halos during fungus-mineral interactions. This process is vital because fungi typically grow attached to various mineral surfaces in nature. According to the changes of thickness of the fungal cell and EPS layers during the Trichoderma guizhouense NJAU 4742 and hematite cultivation experiments in this study, we found that fungal biomineralization could trigger the formation of EPS layers. Fe-dominated nanominerals, aromatic C (283-286.1 eV), alkyl C (287.6-288.3 eV), and carboxylic C (288.4-289.1 eV) were the dominant chemical groups on the EPS layers, as determined by nanoscale secondary ion mass spectrometry (NanoSIMS), high-resolution transmission electron microscope (HRTEM), and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Further, evidence from Fe K-edge X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopy (XPS) spectra indicated that oxygen vacancy (OV) was formed on the Fe-dominated nanomineral surface during fungus-mineral interactions, which played an important role in catalyzing H2O2 decomposition and HO* production. Taken together, the intrinsic peroxidase-like activity by reactive oxygen species (ROS) could modulate the Fe-dominated nanominerals formation in EPS layers to newly form a physical barrier between the cell and the external environments around hyphae, providing novel insights into the effects of ROS-mediated fungal-mineral interactions on fungal nutrient recycling, attenuation of contaminants, and biological control in nature environments.

Direct colour printing on zirconia using 222 nm UV-C photons.

OBJECTIVES: To proof the feasibility of direct colour printing on 3Y-TZP using 222 nm UV-C through investigating the degree and durability of the colour changes, and testifying whether surface, mechanical and biological properties are influenced by the treatment. METHODS: 222 nm UV-C light (Irradiance: 1.870 mW/cm2) was used to treat 3Y-TZP for durations from 15 min to 24 h. ΔE*, TP, crystalline structure, surface morphology, Sa, BFS and biological activities were investigated before and after irradiation. SPSS 28.0 was used for statistical analysis (α = 0.05). RESULTS: 222 nm UV-C irradiation was capable to shade white 3Y-TZP into tooth colours. With the increase of ΔE*, TP decreased, such that the longer the irradiation time, the higher the ΔE* (logarithmic relationship) and lower the TP. Despite the induced optical changes being prone to fade, the process can be predicted by inversely proportional relationships between ΔE*, TP and the testing points. The treated surface exhibited enhanced hydrophilicity, while the recovery phenomenon was observed. Other properties were not altered by the treatment. SIGNIFICANCE: This is the seminal study demonstrating the feasibility of direct colour printing on 3Y-TZP using 222 nm UV-C. The new relationship between the colour centre and Eg of 3Y-TZP was established, whereas the induced optical changes were stabilised after a certain period and were highly predictable by controlling the irradiation periods. The irradiation was only correlated to the electron excitation and oxygen vacancies, and would not lead to any changes of other properties. A simple, safe and promising approach to achieve satisfactory colours on 3Y-TZP in clinical practice can be developed.

Mechanisms of Thermal Decomposition in Spent NCM Lithium-Ion Battery Cathode Materials with Carbon Defects and Oxygen Vacancies.

Resource recovery from retired electric vehicle lithium-ion batteries (LIBs) is a key to sustainable supply of technology-critical metals. However, the mainstream pyrometallurgical recycling approach requires high temperature and high energy consumption. Our study proposes a novel mechanochemical processing combined with hydrogen (H2) reduction strategy to accelerate the breakdown of ternary nickel cobalt manganese oxide (NCM) cathode materials at a significantly lower temperature (450 °C). Particle refinement, material amorphization, and internal energy storage are considered critical success factors for the accelerated decomposition of NCM cathode materials. In our proposed approach, NCM cathode materials can develop active sites with carbon defects (Cv) and oxygen vacancies (Ov), which improve the reduction and breakdown of H2. The adsorbed H2 on the surface of NCM decomposes into H* and combines with oxygen to form OH species, which can be facilitated by Ov via the enhanced charge transfer. The introduced Cv can enhance H2 cracking and generate *C-H species to promote the thermal decomposition of NCM. The presence of defects proves to foster the preferential reduction of Mn(IV) by H2, leading to a lower activation energy for the NCM decomposition (from 139 to 110 kJ/mol) with less H2 consumption. Life cycle assessment suggests a reduction of 4.42 kg CO2 eq for the recycling of every 1.0 kg of retired batteries. This study can promote material circularity and minimize the environmental burden of mining technology-critical metals for a low-carbon transition.

Electrocatalytic conversion of nitrate to ammonia on the oxygen vacancy engineering of zinc oxide for nitrogen recovery from nitrate-polluted surface water.

Nitrate pollution in surface water poses a significant threat to drinking water safety. The integration of electrocatalytic reduction reaction of nitrate (NO3RR) to ammonia with ammonia collection processes offers a sustainable approach to nitrogen recovery from nitrate-polluted surface water. However, the low catalytic activity of existing catalysts has resulted in excessive energy consumption for NO3RR. Herein, we developed a facile approach of electrochemical reduction to generate oxygen vacancy (Ov) on zinc oxide nanoparticles (ZnO1-x NPs) to enhance catalytic activity. The ZnO1-x NPs achieved a high NH3-N selectivity of 92.4% and NH3-N production rate of 1007.9 h-1 m-2 at -0.65 V vs. RHE in 22.5 mg L-1, surpassing both pristine ZnO and the majority of catalysts reported in the literature. DFT calculations with in-situ Raman spectroscopy and ESR analysis revealed that the presence of Ov significantly increased the affinity for the (nitrate) and key intermediate of (nitrite). The strong adsorption of on Ov decreased the energy barrier of potential determining step ( →*NO3) from 0.49 to 0.1 eV, boosting the reaction rate. Furthermore, the strong adsorption of on Ov prevented its escape from the active sites, thereby minimizing by-product formation and enhancing ammonia selectivity. Moreover, the NO3RR, when coupled with a membrane separation process, achieved a 100% nitrogen recycling efficiency with low energy consumption of 0.55 kWh at a flow rate below 112 mL min-1 for the treatment of nitrate-polluted lake water. These results demonstrate that ZnO1-x NPs are a reliable catalytic material for NO3RR, enabling the development of a sustainable technology for nitrogen recovery from nitrate-polluted surface water.

Spectroscopic Analysis of Electrical Phenomena and Oxygen Vacancy Generation for Self-Aligned Fully Solution-Processed Oxide Thin-Film Transistors.

This work unveils critical insights through spectroscopic analysis highlighting electrical phenomena and oxygen vacancy generation in self-aligned fully solution-processed oxide thin-film transistors (TFTs). Ar inductively coupled plasma treatment was conducted to fabricate an amorphous indium zinc oxide (a-InZnO) TFT in a self-aligned process. Results showed that the Ar plasma-activated a-InZnO regions became conductive, which means that a homogeneous layer can act as both channel and electrode in the device. Several techniques were employed to probe specific aspects of the source-drain-channel interface in the fully solution-processed TFTs. X-ray absorption near-edge structure and Extended X-ray absorption fine structure were conducted to investigate the existence of oxygen vacancies, which is the main driving factor in inducing a conductive region. X-ray photoelectron spectroscopy was also used to explain the oxygen refilling mechanism. Ultraviolet Photoelectron Spectroscopy was conducted to analyze the valence band maximum and work function. Integration of these results facilitated the construction of the energy band diagram at the interface, wherein a Schottky barrier height of ∼0.37 eV was observed. By leveraging these techniques, insights into the electronic properties and performance of next-generation transistors are gained, enabling their future widespread adoption.

Boost Electrocatalytic Activity of La0.6Sr0.4Co0.2Fe0.8O3-δ Air Electrode Prepared by High-Temperature Shock for Solid Oxide Electrochemical Cells.

High-temperature shock (HTS) is an emerging material synthesis technology with advantages, such as rapid processing, low energy consumption, and high controllability. This technology can prepare ultrafine nanoparticles with uniform particle size distribution and introduce additional oxygen vacancies, offering significant potential for the preparation of key materials for solid oxide electrochemical cells (SOCs). In this study, the La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) air electrode was successfully prepared using HTS technology. Compared to the conventional muffle furnace calcination, the HTS-prepared LSCF exhibits a larger specific surface area and a higher oxygen vacancy concentration, and it demonstrates significant improvements in performance. The oxygen ion conducting SOC (O-SOC) with the HTS-LSCF air electrode achieved a peak power density (PPD) of 960 mW cm-2 and a current density of 0.38 A cm-2 (at 1.3 V) at 700 °C. Meanwhile, the proton conducting SOC (P-SOC) with HTS-LSCF air electrode reached a PPD value of 1.34 W cm-2 and a current density of 3.43 A cm-2 (at 1.3 V) at 700 °C. Additionally, the P-SOC with HTS-LSCF air electrode showed no significant degradation during over 200 h of long-term testing, reflecting the excellent stability of HTS-LSCF. This work provides a fast, efficient, and economical approach for synthesizing high-performance, high-stability SOC air electrode materials.

Simple and low-cost colorimetric method for quantification of surface oxygen vacancy in zinc oxide.

Zinc oxide (ZnO) nanoparticles with surface oxygen vacancy (OV) was found to catalyze the colorimetric reaction of 3,3',5,5'-tetramethylbenzidine (TMB)-H2O2, and the absorbance of this TMB-H2O2-ZnO system was strongly dependent the OV concentration on surface of ZnO. By taking advantage of this phenomenon, one colorimetric method was proposed for quantifying surface OV in ZnO. The surface OV amount obtained through this colorimetric method matched well with that obtained through X-ray photoelectron spectroscopy (XPS). This colorimetric method doesn't need any advanced instruments, and can be completed in any an ordinary laboratory. This colorimetric method for detecting surface OV amount was simple, rapid (about 15 min) and low-cost.