Introduction Of Oxygen Vacancies Research Articles

Selective oxidation of methane to C2+ products over Au-CeO2 by photon-phonon co-driven catalysis

Direct methane conversion to high-value chemicals under mild conditions is attractive yet challenging due to the inertness of methane and the high reactivity of valuable products. This work presents an efficient and selective strategy to achieve direct methane conversion through the oxidative coupling of methane over a visible-responsive Au-loaded CeO2 by photon-phonon co-driven catalysis. A record-high ethane yield of 755 μmol h−1 (15,100 μmol g−1 h−1) and selectivity of 93% are achieved under optimised reaction conditions, corresponding to an apparent quantum efficiency of 12% at 365 nm. Moreover, the high activity of the photocatalyst can be maintained for at least 120 h without noticeable decay. The pre-treatment of the catalyst at relatively high temperatures introduces oxygen vacancies, which improves oxygen adsorption and activation. Furthermore, Au, serving as a hole acceptor, facilitates charge separation, inhibits overoxidation and promotes the C-C coupling reaction. All these enhance photon efficiency and product yield.

Oxygen vacancies are generated in the inner layer of the core-shell structure by in-situ electrochemical activation to promote electrochemical energy storage

Alkaline zinc ion batteries have attracted attention as potential energy storage devices but remain challenging due to the low utilization rate of active substances, poor conductivity, and few active sites. In order to solve these shortcomings, we grow ultrathin nickel-cobalt layered double hydroxides (NiCo LDH) by electrodeposition on Co3O4 surfaces, and generated abundant oxygen vacancies in the inner layer of the core-shell structure by electrochemical method. The special core-shell structure improves the contact between the active material and the electrolyte, bringing a positive effect on ion diffusion and charge transfer during the energy storage process. At the same time, the abundant oxygen vacancies not only effectively improve the conductivity and the number of active sites of the material, but also improve the valence state conversion ability of the cobalt element. As expected Co3O4-OV/NiCo LDH exhibits a specific capacity of 338.47 mAh g−1 at a current density of 1 A g−1 and a high average discharge potential of 1.65 V relative to Zn2+/Zn. Furthermore, the characterizations combined with density functional theory (DFT) calculations indicate that the generation of oxygen vacancies improves the conductivity and the number of active sites which results in excellent reversible electrochemical activity. This work not only provides new insight into designing advanced electrodes by introducing oxygen vacancies but also opens up avenues for the development of high-performance zinc-cobalt batteries.

Regulation of surface oxygen vacancy of Cu-CeO2/TiO2 heterostructures via fast Joule heating method for enhanced CO2 electrochemical reduction

Strict control of carbon emissions is crucial for expediting the achievement of carbon neutrality. However, the current CO2RR electrocatalytic exhibits numerous shortcomings that impede the enhancement of catalytic activity. Issues such as lengthy catalyst preparation times, and high levels of precious metal content. Additionally, the aggregation of ultrafine nanoparticles contributes to a rapid deterioration in catalytic performance. Herein, a Joule-heating method is efficiently utilized to synthesize heterostructures nano-catalysts for CO2 electroreduction on carbon cloth substrates. This method takes advantage of the thermoelectric coupling of the carbon cloth to achieve carbothermal reduction, while also regulating phase composition and introduction of oxygen vacancies. The Cu-CeO2/TiO2/CC catalyst synthesized in this method showed a current density in CO2 of −32 mA·cm−2 at −1.0 V (vs. RHE). Notably, this catalyst demonstrated high CO selectivity and Faraday efficiency (FECO) of up to 82.5 % at a low potential of −0.3 V (vs. RHE). Optimal electrochemical performance is achieved at a power of 40 W. The ultra-fast temperature change process prevented the agglomeration of catalyst particles and facilitated the construction of a stable heterogeneous interface with a high oxygen vacancy concentration. In conclusion, this study presents a promising approach, particularly for the rapid preparation of low-cost, highly selective non-precious metal electrocatalysts.

Synergistic enhancement of singlet oxygen generation in Au and oxygen vacancy co-modified Bi2MoO6 ultrathin nanosheets for efficient ciprofloxacin degradation

Solar-driven molecular oxygen activation (MOA) is crucial for generating reactive oxygen species (ROS) for pollutant degradation, while the low activation efficiency greatly weakens the degradation efficiency. Herein, oxygen vacancies (OVs) and Au nanoparticles are co-introduced into Bi2MoO6 (ABMOH) to enhance the photocatalytic activity of Bi2MoO6 (BMO), thereby promoting MOA efficiency. Density functional theory demonstrates that the introduction of OVs not only improves the molecular oxygen adsorption on BMO, and but also strengthens the O-O bond dissociation of molecular oxygen, which is beneficial to MOA. Meanwhile, the unique localized surface plasmon resonance effect of Au nanoparticles immensely increases the photo-absorption capacity. Crucially, both OVs and Au nanoparticles work as “electron traps” to capture photogenerated electrons, thereby accelerating charge transfer. Based on the advantage of OVs and Au nanoparticles, ABMOH displays excellent MOA efficiency, and the degradation rate constant of ciprofloxacin (CIPF) by ABMOH-4 is 3.62-fold higher than BMO. Free radical trapping experiment and electron spin resonance suggest that singlet oxygen (1O2) can be selectively formed in the ABMOH system for CIPF degradation, and superoxide radical (•O2–) conversion and energy transfer are two pathways for 1O2 formation. This investigation serves as a beacon for the strategic design of high-performance and stable photocatalysts for MOA activation, paving the way for advancements in environmental remediation.

Revealing the Mechanism of Converting CO2 into Methanol by the Cu2O and Oxygen Vacancy on MgO: Experiments and Density Functional Theory.

Given the great significance of defect and Cu compounds for the reduction of CO2 as well as the few reaction mechanisms of converting CO2 into different hydrocarbons, the effects of oxygen vacancies and Cu2O on the reduction of CO2 were thoroughly investigated, and possible mechanisms were also proposed. A series of Cu2O/Ov-MgO catalysts were synthesized for photothermal catalytic reduction of CO2 to methanol under visible-light irradiation, among which the 7%Cu2O/Ov-MgO composite exhibited the best reduction activity and the yield of methanol was 19.78 μmol·g-1·h-1. The successful composite of Cu2O and Ov-MgO can yield a loose and porous nanosheet, uniform distribution, favorable absorbance and photoelectric performance, and increased specific surface area and adsorption ability of CO2, which are all vital to the adsorption and conversion of CO2. The introduction of oxygen vacancy and Cu2O not only promotes the adsorption of CO2 but also provides more electron-triggered CO2 activation. Density functional theory (DFT) calculation was also performed to reveal the reaction mechanism for effective enhanced CO2 reduction to ethanol or methanol by the comparison of CuO/MgO and Cu2O/Ov-MgO composites, illustrating the reaction pathways of different products. By comparing the key steps in determining the selectivity of C1 or C2, the kinetic barriers of obtaining CH3OH for the Cu2O/Ov-MgO composite with CH3OH as the main product were found to be lower than those of generating CH2*, while the opposite is true for CuO/MgO composites, whereby it may be easier to obtain more C2 products. These insights into the reaction mechanism of converting CO2 into different hydrocarbons are expected to provide guidance for the further design of high-performance photothermal catalytic CO2 reduction catalysts.

Achieving Superior Cyclability Pouch Cells with Oxygen Vacancy-Moderated P'2/P3 Hybrid Layered Sodium Cathode Materials.

Layered P2-type sodium manganese oxide has emerged as a promising cathode candidate for sodium-ion batteries due to its appealing cost-effectiveness and high discharge voltage. However, its practical capacity within the voltage range of 2.0-4.0 V (vs Na+/Na) is relatively low, and its rate capability is hampered by the adverse charge/vacancy ordering during charge/discharge. In this study, a layered P'2/P3 mixed-phase Na0.8-aMn0.675Ni0.225Li0.1O2-x cathode with high (003) crystal plane intensity was designed by introducing oxygen vacancies to P2-structured materials. Aided by these advantages, the hybrid cathode material demonstrates impressive structural and thermal stability and faster Na-ion diffusion kinetics compared to a regular P2 material. Half-cell shows an initial discharge capacity retention of 101 mA h/g at 12 mA/g and 92.25% retention after 500 cycles at 120 mA/g. In combination with a hard carbon anode, the 0.5 A h pouch cell achieved a prevailing capacity retention of 95.2% after 2600 cycles at 36 mA/g. This work opens new dimensions for layered cathode materials with the aim of achieving superior cyclabilities.

Enhanced broadband infrared radiation from rare earth orthochromites for High-Temperature radiative heat transfer

The development of broadband, high-performance infrared radiation materials is crucial for energy conservation and applications in aerospace and industrial sectors. Rare earth orthochromites, such as PrCrO3, exhibit good thermal stability and high infrared emissivity beyond the 6 μm wavelength range. However, their large bandgap limits their infrared emissivity before 6 μm, significantly impacting their potential applications. Herein, we have successfully enhanced the thermal emissivity of PrCrO3 by manipulating oxygen vacancies (OV) and accompanying impurity levels, leading to the synthesis of five rare earth orthochromites. Compared with pristine PrCrO3, co-doping of Ca, Co, and Mn introduced oxygen vacancies (OV) and impurity energy levels, effectively reducing the band gap and improving emissivity in the wavelengths below 6 μm. In particular, the infrared emissivity of (Pr0.3Y0.3Ca0.4)CrO3 in the wavelengths of 0.78–2.5 μm reaches 0.89, which is double than that of pristine PrCrO3. Furthermore, its thermal stability is excellent, as demonstrated by thermal shock experiments at 1500 ℃ for five cycles. More importantly, the developed orthochromites can be applied as a coating on substrates such as alumina ceramic sheets, exhibiting an average infrared emissivity of 0.95 and remarkable radiative heat transfer capability. This research contributes to the advancement of high-performance infrared radiation materials by vacancy engineering.

Transition metal in-situ doped BiOBr: Introducing oxygen vacancies to enhance hydroxyl radical generation for improved photocatalytic degradation of toluene

Photocatalytic oxidation for the removal of volatile organic compounds (VOCs) is one of the most effective and environmentally friendly means, and hydroxyl radicals with strong oxidation ability play an important role in the photocatalytic degradation of VOCs. In this paper, by selecting different transition metals (M=Co, Ni, Cu, Fe) for in situ doping modification of layered bismuth bromide oxide (BiOBr). It was found that among the catalysts Co-doped BiOBr had the highest photocatalytic degradation efficiency and mineralization rate (with 81.7 % and 64.0 %, respectively), and were significantly higher than those of BiOBr (with 51.4 % and 19.4 %, respectively). Experimental results and theoretical calculations confirmed that transition metal in situ doping modification can induce the generation of oxygen vacancy defects, while being more favorable to the adsorption and activation of H2O molecules, which leaded to the generation of a large number of hydroxyl radicals with stronger oxidative capacity and achieved the efficient photocatalytic degradation of toluene.

Defect engineering in SnO2 catalysts for the organic oxidation reaction

Defect engineering in metal oxides is an effective approach for improving advanced oxidation processes. Herein, we report that regulating the defect types present on SnO2 enables deconvolution of their distinct effects on organic oxidation. Nitrogen annealing created E′δ center and non-bridging oxygen hole center (NBOHC) defects, while optimum hydrogenation introduced oxygen vacancies, significantly enhancing catalytic oxidation performance. Based on spectroscopic analysis, extended hydrogenation times passivated NBOHCs and formed new types of defects, such as electrons trapped in oxygen vacancies, which are less catalytically active in comparison with NBOHCs. DFT indicated that oxygen vacancies lower the energy barrier for oxygen activation as well as activation of the C-H bonds in formic acid, corroborating the experimental results of enhanced catalytic activity in samples with optimized defect concentrations. The current work advances understanding of the roles different defects play in enhancing organic oxidation in the ongoing search for efficient materials for oxidation reactions.

PAN-assisted preparation of Bi2MoO6 with enhanced photocatalytic CO2 reduction performance

In this study, to improve photocatalytic CO2 reduction efficiency of Bi2MoO6-based photocatalysts, Bi2MoO6 (BMO) was synthesized via a solvothermal method with the assistance of polyacrylonitrile (PAN). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques were utilized to evaluate the microstructures, phases, and elemental compositions of the samples. Additionally, the separation and migration efficiency of photogenerated charge pairs during the photocatalytic process were analyzed in detail using surface photovoltage spectroscopy (SPS), photoluminescence spectrum (PL), transient photocurrent density (TPR), and electrochemical impedance spectroscopy (EIS). In comparison with the reference sample, the specific surface area of 2 % BMO (mass ratios of PAN/Bi(NO3)3·5H2O is 2 %) has been increased to 39.6 m2/g, which increases by 0.9 times compared to the reference sample. The successful introduction of oxygen vacancies (OVs) in Bi2MoO6 was confirmed by low-temperature electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS), and suitable OVs is favorable for separation and migration of the photogenerated carriers. The experimental results indicate that the separation efficiency of photogenerated carriers in the PAN-BMO photocatalyst is significantly boosted in contrast to the reference sample. Furthermore, all photocatalysts exhibit higher photocatalytic CO2 reduction activity than the reference sample. It is noteworthy that the 2 % BMO sample shows the highest photocatalytic CO2 reduction activity, and the average photocatalytic CO2 reduction yield over the 2 % BMO reaches 2.16 μmol g−1 h−1, which is 2.25 times higher than that on the reference sample (0.96 μmol g−1 h−1). In view of the findings, photocatalytic CO2 reduction mechanism for BMO with OVs was rationally proposed.

Constructing oxygen vacancies by selective anion doping in high entropy perovskite oxide for water splitting

High entropy perovskite oxide (HEPO) is a potential electrocatalyst for the oxygen evolution reaction (OER), but insufficient activity remains a problem. Oxygen vacancies can activate the lattice oxygen to induce the lattice oxygen-mediated mechanism (LOM), which can avoid the kinetic limitation present in adsorbate evolution mechanism (AEM), thereby improving the OER activity. Herein, we select the appropriate doping element (S) through analysis of ionic radius, electronegativity, and oxygen vacancy formation energy, and report an effective two-step oxygen vacancy strategy for introducing oxygen vacancies into HEPO through electrospinning and sulfurization treatment. This strategy optimizes the eg orbital filling electron number and significantly increases the active area, oxygen vacancy content and electroconductivity. Furthermore, the apparent pH dependence and the TMA+ inhibition phenomenon suggest the involvement of the LOM. Consequently, the resulting S/LMO-E has a lower overpotential (314 mV at 10 mA cm−2) and faster kinetics, and shows excellent stability. Meanwhile, the water splitting is achieved at 1.59 V to afford 10 mA cm−2 current density for S/LMO-E⎪⎢Pt/C, which is smaller than that of RuO2⎪⎢Pt/C (1.62 V). This work provides an attractive OER electrocatalyst for efficient water splitting to produce renewable hydrogen and opens a new way for the design of effective and stable high entropy material electrocatalysts.

Defects tune the acidic strength of amorphous aluminosilicates

Crystalline zeolites have high acidity but limited utility due to microporosity, whereas mesoporous amorphous aluminosilicates offer better porosity but lack sufficient acidity. In this work, we investigated defect engineering to fine-tune the acidity of amorphous acidic aluminosilicates (AAS). Here we introduced oxygen vacancies in AAS to synthesize defective acidic aluminosilicates (D-AAS). 1H, 27Al, and 17O solid-state nuclear magnetic resonance (NMR) studies indicated that defects induced localized structural changes around the acidic sites, thereby modifying their acidity. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy studies substantiated that oxygen vacancies alter the chemical environment of Brønsted acidic sites of AAS. The effect of defect creation in AAS on its acidity and catalytic behavior was demonstrated using four different acid-catalyzed reactions namely, styrene oxide ring opening, vesidryl synthesis, Friedel-Crafts alkylation, and jasminaldehyde synthesis. The defects played a role in activating reactants during AAS-catalyzed reactions, enhancing the overall catalytic process. This was supported by in-situ FTIR, which provided insights into the molecular-level reaction mechanism and the role of defects in reactant activation. This study demonstrates defect engineering as a promising approach to fine-tune acidity in amorphous aluminosilicates, bridging the porosity and acidity gaps between mesoporous amorphous aluminosilicates and crystalline zeolites.

Influence of Nb Doping on the Performance of Oxygen Reduction Reaction on TiO2 in Acidic Environmental

Polymer electrolyte fuel cells (PEFCs) have attracted attention as one of the next-generation power sources that are environmentally friendly. However, the high manufacturer's costs, short service life, and insufficient cell performance are solved to realize widespread commercialization. A non-platinum group metal catalyst is relatively low in cost and highly durable. In particular, the oxides of group 4 and 5 elements were reported to show high oxygen reduction reaction (ORR) activity and durability. Their oxides are considered dominant candidates for the non-platinum group metal catalysts, although they have a fateful flaw that their ORR activity is clearly poorer than traditional platinum-supported carbon catalysts. It was reported that introducing oxygen vacancies and other transition metals into the crystal structure of 4- and 5-group metal oxides effectively enhanced the ORR activity. The active site of 4- and 5-group metal oxides is unclear despite it being well-known that the oxygen vacancies and dopant atoms are related to its ORR activity. It is now indicated that candidates of active site were the oxygen vacancies around the dopant atom and the crystal distortion. However, it is hard to separate their effects because both dopant atoms and oxygen vacancies distort the local crystal structure. On the other hand, identifying the ORR active site leads to obtaining the catalyst design with high ORR activity. We focused on the oxide nanosheet, the simplest structure formed by a six-coordinate octahedral, as the model electrode. The thickness of oxide nanosheets is about 1 nm, and forming a single layer on a substrate is relatively easy. Thus, it was expected that the electron conductivity was guaranteed enough by the tunnel effect. This study employed titanium oxide nanosheets (TiO2ns) as the model catalyst and niobium as a dopant to investigate the effect of dopant atoms on ORR activity. The ratio of Nb/Ti in the prepared model electrode was 0/1, 1/1, and 2/1. In addition, the oxygen vacancies were introduced into all prepared electrodes to study the impact of oxygen vacancies on ORR activity at each Nb/Ti ratio. The thickness of Nb-doped TiO2ns (Nb-TiO2ns) was about 1.2 nm for the 1/1 ratio and slightly thicker for the 0/1 ratio. In contrast, the thickness of the 2/1 ratio of Nb-TiO2ns was about two times thicker than the 1/1 ratio. The thicknesses of Nb-TiO2ns in each ratio were increased by the reduction treatment to introduce the oxygen vacancies. One reason for this thickness increase may be related to the phase transition into the anatase structure. ORR activity was evaluated from the on-set potential of ORR (E ORR) measured at the step scan with 3 minutes step width. E ORR was slightly elevated with Nb doping. The ion radii of Nb and Ti atoms are 3 pm different when it is assumed that both ions are six-coordinated and their valence is Nb5+ and Ti4+. These results showed that the crystal structure distortion probably has a slight but positive effect on ORR activity.After the reduction treatments, the E ORR of the 0/1 ratio of Nb-TiO2ns increased and was the same as that of the 2/1 ratio. The introduction of oxygen vacancies certainly enhanced the ORR activity of the 0/1 ratio of Nb-TiO2ns. The oxygen vacancies are thought to be necessary to enhance the ORR activity, although the reduction condition wasn’t optimized for the Nb-doped samples.From the above results, we consider that the active site is the oxygen vacancy site rather than the crystal distortion site at this time.

Refining Mn(III) Active Sites in MnO2-Based Self-Assembled Electrodes Via Oxygen Vacancy Induction to Enhance Oxygen Reaction Performance in Zinc-Air Batteries

Rechargeable zinc-air batteries are considered as a promising candidate for next-generation electrochemical energy conversion devices due to their safety, low cost, and high theoretical capacity/ energy density. Over the past few decades, α-MnO2-based electrodes have demonstrated their excellent performance and competitiveness in oxygen catalytic reactions. (1) According to eg filling theory, Mn(III) (t2g3eg1) sites in [MnO6] octahedral unit deliver superior bifunctional activity compared to Mn(II) (t2g3eg2) and Mn(IV) (t2g3eg0) sites.(2) However, the presence of unpaired single electrons of the Mn(III) site leads to low thermodynamic stability. Introducing oxygen vacancies to promote the electron rearrangement of the [MnO6] unit is a promising approach for enhancing the durability of Mn(III) active sites. Herein, we construct an oxygen-vacancy-enhanced MnO2-based electrode via a self-assembly process (NiCo2O4-MnO2@Ni foam). The intrinsic oxygen catalytic activity of NiCo2O4-MnO2@Ni foam is significantly improved by forming abundant highly stable Mn(III) active sites, which accelerate the mass transfer ability. As expected, the NiCo2O4-MnO2@Ni foam shows good bifunctional activity with a low overpotential of 0.69 V. The zinc-air battery assembled by NiCo2O4-MnO2@Ni foam exhibits a high peak power density of 576 mW cm-2, surpassing that of the Pt/C-Ir/C electrode. Additionally, benefiting from its stable flower-shaped hierarchical structure, the self-assembled electrode demonstrates long-term charge-discharge cycling stability, which lasts over 800 hours. This work provides innovative insights into enhancing MnO2-based electrodes by oxygen vacancy introduction.References N. Xu, Q. Nie, L. Luo, C. Z. Yao, Q. Gong, Y. Liu, X. Zhou, and J. Qiao, ACS applied materials & interfaces (2018).Z. Yin, R. He, H. Xue, J.-M. Chen, Y. Wang, X. Ye, N. Xu, J. Qiao and H. Huang, Energy Materials (2022).

Modified Ta2O5-x prepared by NaBH4 reduction for enhance its photocatalytic activity

The generation of oxygen vacancies assumes a pivotal role in the photocatalytic degradation of antibiotics. Surface oxygen vacancies serve as deterrents to the recombination of photogenerated carriers, thereby augmenting photocatalytic efficiency. In this work, the NaBH4 reduction technique was adopted to introduce oxygen vacancies onto the surface of Ta2O5-x, thus enhancing its photocatalytic powers. Remarkably, the photocatalytic activity of the modified Ta2O5-x-0.5 M samples exhibited significant improvement upon treatment with NaBH4 solution at varied concentrations. Characterization of the modified Ta2O5-x samples was conducted using a suite of techniques including XRD, FT-IR, UV–vis DRS, ESR, XPS, and EPR. Notably, the EPR spectrum provided compelling evidence of the presence of oxygen vacancies, affirming their existence on the surface of the modified Ta2O5-x samples. To further corroborate the formation of oxygen vacancies, tetracycline (TC) solution was employed as a simulated pollutant, revealing a marked enhancement in visible light catalytic activity through experimental observations. The findings elucidate that the defect sites engendered by oxygen vacancies primarily enhance the efficiency of electron-hole pair separation and facilitate greater absorption of visible light, thereby amplifying photocatalytic activity. The modification of Ta2O5-x samples by NaBH4 reduction predominantly facilitates the introduction of oxygen vacancies on the surface, consequently bolstering photocatalytic performance. This exemplifies a noteworthy approach for significantly enhancing the photocatalytic activity of Ta2O5-x, providing valuable insights for future design strategies.

Enhanced electrical performance in graphene field-effect transistors through post-annealing of high-k HfLaO gate dielectrics

High-k gate dielectrics have attracted a great deal of attention in the investigation of transistors due to their unique properties such as superior gate controllability. However, their integration into graphene field-effect transistors (GFETs) remains problematic and the physical mechanisms governing the performance of these devices are still not fully understood. In this study, the effects of post-annealing on GFETs utilizing the high-k HfLaO ternary oxide as the gate dielectric were comprehensively investigated. The HfLaO film was deposited on top of graphene by magnetron sputtering, and the device performance with various post-annealing temperatures was conducted. It was found that post-annealing temperature can effectively increase the dielectric constant through balancing the oxygen-vacancy defects and moisture absorption. Both the surface morphology of HfLaO and performance of GFETs were investigated, and the fabricated GFETs exhibit notable electrical performance enhancements. Specifically, GFETs with a 200 °C post-annealed HfLaO gate dielectric demonstrate the optimal device performance, featuring a minimal Dirac point voltage (VDirac) of 1.1 V and a minimal hysteresis (ΔVDirac) of 0.5 V. The extracted hole and electron mobilities are 4012 and 1366 cm2/V · s, respectively, nearly one order of magnitude higher than that of GFETs with as-deposited HfLaO. This work outperforms other existing GFETs utilizing high-k gate dielectric and chemical vapor deposition grown graphene in terms of both carrier mobility and on–off ratio. It is also noted that the excessive post-annealing temperature can negatively impact the GFET performance through introducing oxygen vacancies, increasing the surface roughness, lowering the breakdown voltage, and inducing recrystallization.

Enhanced vanadium redox reaction catalytic properties enabled by tunning oxygen vacancy in rutile tio2 coated graphite felt electrodes

Abstract Catalyzing vanadium redox reactions in VRFBs with transition metal oxides is an effective and affordable approach. In this study, the surface electron distribution of TiO2 was regulated by introducing oxygen vacancies into its lattice, enabling the electrode to exhibit outstanding catalytic efficacy in VO2 +/VO2+ and V3+/V2+ redox transformations and suppress the detrimental side reaction (HER and OER) simultaneously. Benefiting from the enhanced catalytic activity and selectivity, the 1000-TiO2-GF electrode sustained a stable operation for 100 cycles at 120 mA cm−2 with no discernible efficiency degradation. The DFT results indicate that oxygen vacancy in TiO2 provides more extra electrons to its neighboring titanium, further strengthening the interaction between the electron-rich titanium and oxygen in VO2 +/VO2+, thus enhancing its catalytic performance. The enhanced catalytic activity for V3+/V2+ on oxygen vacancy-rich TiO2 coating can be attributed to the effective suppression of hydrogen evolution reaction, which can occupy active sites exclusively and produce detrimental H2 bubbles. This insight provides valuable guidance for the innovative design of catalysts in vanadium redox flow batteries.

First-principles studies on the oxygen vacancy formation in α-Na2FePO4F and β-Na2FePO4F

The orthorhombic β-Na2FePO4F has been extensively studied, however, a novel monoclinic α-Na2FePO4F has not been explored sufficiently. Oxygen vacancies (VO) can affect the physical and chemical properties of materials, and oxygen vacancy formation energy reflects the difficulty of VO formation. Using first-principles methods, we have calculated the formation energies of VO and their relevant charge states in both α-Na2FePO4F and β-Na2FePO4F. Our results reveal that charged vacancies (VO+1 or VO+2) are easier to form than neutral vacancies (VO0). The reduction of the Fermi level, the decrease in the oxygen partial pressure, or the increase of the temperature are found to decrease the formation energy of VO. The formation energy of VO in α-Na2FePO4F is slightly lower than that in β-Na2FePO4F. The electronic density of states of α-Na2FePO4F and β-Na2FePO4F suggest that more defect states are introduced into the band gap as the charge states increase. These defect states are mainly the 3d orbitals of the Fe atoms. The introduction of oxygen vacancies distorts the [FeO4F2] octahedra, which affect the charge density distribution and the defect states introduced in the band gap. Significantly, oxygen vacancies have a local impact on the charge density redistribution in both α-Na2FePO4F and β-Na2FePO4F. These findings provide theoretical insights into the formation of oxygen vacancies and the control of oxygen release.

Oxygen-Vacancy-Induced Enhancement of BiVO4 Bifunctional Photoelectrochemical Activity for Overall Water Splitting.

Hydrogen generation via photoelectrochemical (PEC) overall water splitting is an attractive means of renewable energy production so developing and designing the cost-effective and high-activity bifunctional PEC catalysts both for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) has been focused on. Based on first-principles calculations, we propose a feasible strategy to enhance either HER or OER performance in the monoclinic exposed BiVO4 (110) facet by the introduction of oxygen vacancies (Ovacs). Our results show that oxygen vacancies induce charge rearrangements, which enhances charge transfer between active sites and adatoms. Furthermore, the incorporation of oxygen vacancies reduces the work function of the system, which makes charge transfer from the inner to the surface more easily; thus, the charges possess stronger redox capacity. As a result, the Ovac reduces both the hydrogen adsorption-free energy (ΔGH*) for the HER and the overpotential for the OER, facilitating the PEC activity of overall water splitting. The findings provide not only a method to develop bifunctional PEC catalysts based on BiVO4 but also insight into the mechanism of enhanced catalytic performance.

Vertical VOPO4·2H2O Nanosheets with Richly Exposed (200) Plane Enable Fast-Kinetics High-Mass-Loading Cathodes for Zn-Ion Batteries.

Extending the layer spacing of the (001) planes to regulate the mobility of Zn2+ is widely adopted to optimize the performance of VOPO4·2H2O cathode for zinc-ion batteries. However, the unique function originating from other planes is often neglected. Herein, an effective in situ conversion methodology is proposed for the synthesis of the (200) oriented growth of vertical VOPO4·2H2O nanosheets with oxygen vacancies (VOd-VOPO4). Theoretical simulation and ex situ characterizations collaboratively demonstrate that the richly exposed (200) plane with tetragonal channels can offer quick pathways for in-layer and cross-layer migration of Zn2+, exhibiting enhanced transfer kinetics with improved reversible capacity. Meanwhile, efficient electron migration in VOd-VOPO4 is guaranteed by the introduction of oxygen vacancies. Thus, the as-prepared VOd-VOPO4 harvests exceptional discharge capacity, impressive rate capability, and remarkable long-cycle stability at high mass loading. Notably, the VOd-VOPO4 electrode (15mg cm-2) provides a capacity of 213.5mAhg-1 with an ultrahigh areal capacity of 3.02 mAh cm-2 at 0.1 A g-1, showing great potential for applications. This study highlights the orientated growth strategy for facilitating ion storage and migration, offering novel perspectives on the development of high-performance electrodes and beyond.