Oxygen Vacancy Concentration Research Articles

Self‐Confined Construction of Facet Heterojunction with Tunable Band Alignment for Enhanced Photocatalytic CO2 Reduction

AbstractAlthough crystal facet engineering is extensively studied in energy and environmental technologies, the in‐depth understanding of intrinsic mechanisms governing crystal facet heterojunctions in tuning band alignments is still limited. Here, novel Bi5O7NO3 crystals exposing tailor {080} facets are synthesized via NH4+‐assisted self‐confined construction. It has been confirmed that NH4+ ions selectively adsorb on the {141} facets, inversely inducing the growth of desired {080} crystal facets, while the tailored {080} facets facilitate the generation of oxygen vacancies. The controllable concentration of oxygen vacancies, influenced by different exposed facets, can optimize the relative positions of Fermi levels and shift the photoelectron transfer route between the {141} and {080}‐OV facets from type‐II to S‐scheme, thus triggering rapid charge transport channels and effectively suppressing electron‐hole recombination. DFT calculation verifies that the energy barrier for the *COOH formation on Bi5O7NO3‐{080}‐OV is the lowest, thereby promoting the generation of CO. The well‐designed Bi5O7NO3 crystals with the optimal {080}/{141} facet ratio exhibit a 3.8‐fold enhancement in photocatalytic CO2 reduction, compared to traditional Bi5O7NO3 dominated by the {141} facets. This work offers new insights into the regulation of band alignments at heterointerfaces and the design of high‐efficiency photocatalysts.

Conduction in yttrium iron garnets with nickel dopant: Potential for sensor applications

Doped yttrium iron garnet materials exhibit semiconducting behavior and have potential applications in resistive-based sensors, including thermoresistive and gas sensors. In this study, we synthesized Ni-doped yttrium iron garnet samples using the sol-gel method combined with heat treatment. The crystal structure, morphology, and Ni incorporation into the crystal lattice were investigated using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Raman spectroscopy. The saturation magnetization of the samples in the ground state was measured in a Physical Property Measurement System (PPMS) at 5 K. The experimental magnetic moments deviate significantly from the values calculated based on the cation distribution models, suggesting the occupation of Ni2+ and Fe2+ at the octahedral and tetrahedral sites, respectively, with the latter due to oxygen vacancies. We investigated the resistivity, magnetoresistance effect, and hydrogen sensing properties to elucidate the conduction mechanism. At room temperature, the resistivity of the samples decreased sharply as the oxygen vacancy concentration increased, from ∼108 Ωcm in sample x = 0 to ∼106 Ωcm in sample x = 0.08. The resistance of the samples increased when exposed to hydrogen gas, supporting the prediction from the magnetization data that the samples exhibit n-type semiconductor characteristics. The samples showed good sensitivity to H2 gas. At 250°C, sample x = 0.08 exhibits a response of S =11.5, the response time (τres. ∼8 s), and recovery time (τrec. ∼22 s) at 100 ppm hydrogen concentration.

An efficient Au/ZnO catalyst for the photocatalytic conversion of methane to formaldehyde

The photocatalytic oxidation of methane to value-added chemical products under mild conditions is crucial for resource utilization and environmental protection. However, inefficient generation of reactive oxygen species partially limits methane activation. To tackle this issue, we have developed highly dispersed Au-modified ZnO nanosheets through photo-deposition method for the photocatalytic oxidation of methane to formaldehyde. The optimized Au0.1/ZnO catalyst (0.1 wt% Au on ZnO) achieves a HCHO yield of 19.14 μmol h−1 with a selectivity of 87.94 %. Electron paramagnetic resonance, Raman, X-ray photoelectron spectroscopy and density functional theory show that Au enhances the concentration of oxygen vacancies (OVs) in ZnO. This enhancement is attributed to a strong interaction between Au and ZnO, which facilitates the transfer of electrons from the ZnO surface to Au. Under irradiation, Au and OVs function as hole and electron acceptors, respectively. This interaction promotes carrier separation, reduces charge recombination, enhances oxygen adsorption, and effectively generates reactive oxygen species, such as ·OH. Subsequently, CH4 is oxidized to ·CH3 by holes from Au. Concurrently, O2 is reduced by electron from OVs, following the pathways O2 → OOH→H2O2 → ·OH. The rapid oxidation of CH3OH by ·CH3 and ·OH results in the formation of HCHO.

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.

Crystal Structures and Piezoelectric Properties of Quenched and Slowly-Cooled BiFeO3-BaTiO3 Ceramics.

The BiFeO3-BaTiO3 (BF-BT) ceramics were here prepared through the solid-state reaction of Bi2O3, Fe2O3 and nano-sized BT powders. The crystal structures and piezoelectric properties were investigated in both quenched (AQ) and slowly cooled (SC) 0.7BF-0.3BT ceramics. Prior work has shown that rhombohedral and pseudo-cubic phases coexist in 0.7BF-0.3BT ceramics. In this work, the crystal structure of the pseudo-cubic phase was refined as a non-polar orthorhombic Pbnm phase in the SC sample and as a polar orthorhombic Pmc21 phase in the AQ sample. In addition to a sharp dielectric peak at about 620 °C, corresponding to the Curie temperature of the rhombohedral phase, a broad dielectric peak with strong frequency dispersion and a sharp frequency-independent dielectric peak were observed at around 500 °C in the SC and AQ samples, respectively. We determine that the dielectric anomalies around 500 °C were caused by a relaxor phase transition of the non-polar orthorhombic phase in the SC sample and a ferroelectric-paraelectric phase transition of the polar orthorhombic phase in the AQ sample. The AQ sample showed better ferroelectric and piezoelectric properties than the SC sample. The 0.7BF-0.3BT ceramic slowly cooled in a nitrogen atmosphere showed a well-saturated P-E curve and a similar temperature-dependent dielectric constant as the AQ sample. Our results indicate that large concentrations of oxygen vacancies produce a more distorted polar orthorhombic phase and better piezoelectric properties in the AQ sample than in the SC sample.

Actual reliance of catalytic activities tuned oxygen vacancies on VOx/Ce1-xZrxO2 catalyst for selective oxydehydrogenation of methanol to dimethoxymethane

Metal oxide catalysts like ceria-supported vanadia (VOx/Ce1-xZrxO2) with different Zr contents were prepared by coupling ceria-zirconia solid solution and vanadia. Characterization revealed that the insertion of zirconia into ceria significantly improved catalytic activity due to the generation of more oxygen vacancies and distortion of the composite structure. The oxygen vacancy concentration initially increased with the increase of Zr (x= wt%) and peaked at x=0.7 and then decreased. The reliance of oxygen vacancy concentration in VOx/Ce1-xZrxO2 catalyst on their catalytic activity in methanol oxydehydrogenation was further investigated. Results indicated that oxygen vacancies not only activated oxygen species but also cleaved C–H bonds alongside V5+ active site contained terminal oxygen atoms for cleaving O–H and C–H bonds within the adsorbed methanol. The VOx/Ce0.3Zr0.7O2 exhibited the best catalytic activity with the methanol conversion of 76 % and the dimethoxymethane selectivity of 96 % at 200 ℃ and atmospheric pressure in a fixed-bed reactor.

Depth-Resolved X-Ray Photoelectron Spectroscopy Evidence of Intrinsic Polar States in HfO2-Based Ferroelectrics.

The discovery of ferroelectricity in nanoscale hafnia-based oxide films has spurred interest in understanding their emergent properties. Investigation focuses on the size-dependent polarization behavior, which is sensitive to content and movement of oxygen vacancies. Though polarization switching and electrochemical reactions is shown to co-occur, their relationship remains unclear. This study employs X-ray photoelectron spectroscopy with depth sensitivity to examine changes in electrochemical states occurring during polarization switching. Contrasting Hf0.5Zr0.5O2 (HZO) with Hf0.88La0.04Ta0.08O2 (HLTO), a composition with an equivalent structure and comparable average ionic radius, electrochemical states are directly observed for specific polarization directions. Lower-polarization films exhibit more significant electrochemical changes upon switching, suggesting an indirect relationship between polarization and electrochemical state. This research illuminates the complex interplay between polarization and electrochemical dynamics, providing evidence for intrinsic polar states in HfO2-basedferroelectrics.

High-performance Co-free dual-phase perovskite positrodes for protonic ceramic cells: Zn and Ni-doped BaCe0.2Fe0.8O3-δ system

Protonic ceramic cells (PCCs) can convert the energy between electricity and fuels efficiently, and are attracting increasing attention. However, the development of PCCs is restricted by the lack of proper positrode materials. In this work, we report a Co-free system with a nominal composition of BaCe0.2Fe0.8O3-δ, which is composed of a Fe-rich matrix phase decorated with Ce-rich nanoparticles. The performance of such a dual-phase positrode system is further improved by doping Zn and/or Ni to increase bulk and surficial concentration of oxygen vacancies. The hydration reaction and surficial adsorption of oxygen species are thereby promoted, benefitting the oxygen reduction reaction. The Ni and Zn co-doped composition Ba(Ce0.2Fe0.8)0.85(Ni0.5Zn0.5)0.15O3-δ exhibits lower polarization resistance than the pristine and singly doped systems, enabling the fuel cells to show high peak power densities of 400, 721, and 828 mW cm−2 at 550, 600, and 650 °C, respectively.

UV-assisted preparation of highly selective Ce-doped BiOBr-based triethylamine gas sensors

In this study, the Ce-doped BiOBr gas sensor was prepared for the detection of triethylamine by ultraviolet-assisted deposition. Characterization tests such as EDS and XPS verified the presence of Ce elements. The gas sensing test results show that adding Ce improves the selectivity of BiOBr to triethylamine gas. Moreover, the Ce/BiOBr sensor showed a 141 % improvement in response to 200 ppm of triethylamine at 300 °C compared to the BiOBr sensor. The enhanced sensing performance of Ce/BiOBr is mainly attributed to the increased concentration of oxygen vacancies.

A CuO/MoO3-based SO2 gas sensor with moisture resistance and ultra-fast response at 90°C

Sulfur dioxide (SO2) is a toxic and harmful decomposition product generated during arc discharge or partial discharge in sulfur hexafluoride (SF6) electrical equipment, which can corrode internal pipelines. Detecting SO2 is crucial for assessing the insulation condition of equipment and preventing faults. To overcome the challenges faced by traditional SO2 gas sensors, including high operating temperatures, slow response times, and poor moisture resistance, this paper proposes a novel SO2 gas sensor based on CuO/MoO3. The morphology, composition, and chemical states of the materials were analyzed using different characterization techniques. At 90°C, the S2 sensor (CuO: MoO3=1: 1) exhibited a fast response time (10 s) to 10 ppm SO2 and demonstrated good moisture resistance (a 1 % change in relative humidity (RH) has the same effect on the sensor as 25.9 ppb SO2). The response of the S2 sensor to 100 ppm SO2 was 26.5. Additionally, the voltage sensitivity of the S2 sensor at low (1–10 ppm) and high (10–100 ppm) concentrations are 658.74 mV/ppm and 33.43 mV/ppm, respectively. Therefore, the S2 sensor is more suitable for low concentration conditions. These good sensing characteristics of the S2 sensor are owing to the high content of oxygen vacancies (39.2 %) and the heterojunction effect in the composite material. Additionally, this sensor exhibits excellent anti-interference capabilities, including moisture resistance and high selectivity. Therefore, the CuO/MoO3-based SO2 gas sensor can be effectively applied to detect the decomposition of SF6.

Excellent energy storage performance of Nd-modified lead-free AgNbO3 ceramics via triple collaborative optimization

Lead-free Dielectric capacitors that possess high power density as well as swift charging/discharging speed are in tremendous requirement in pulse/high power fields, but the lower recovery energy density and efficiency restrict their applications. Herein, via triple collaborative optimization, we designed Nd-modified AgNbO3 antiferroelectric ceramics with excellent energy storage performance. First, Nd3+ ions are smaller than Ag+ ions, which effectively inhibits cation displacements and the tilting of oxygen octahedra, leading to an optimized phase composition, the suppressed ferroelectricity and enhanced antiferroelectricity. Second, the valence of Nd3+ ions are higher than that of Ag+ ions, which help to lower the content of oxygen vacancies. Third, the random substitution of Nd3+, extrinsic ions, cause the chemical disorder, thus dwindling the grain size. Both of the latter could boost the breakdown field. Eventually, the synchronously boosted energy density of 7.16 J/cm3 and efficiency of 72 %, together with excellent frequency stability, temperature tolerance, ultrafast charging/discharging time of 45 ns and superhigh power density of 354.2 MW/cm3, are achieved in Ag0.91Nd0.03NbO3. All these merits manifest Nd- AgNbO3 as a promising candidate for lead-free high-power energy storage devices. Our work brings forward a good reference for developing the capabilities of antiferroelectric capacitors.

Surface Reconstruction of High-Voltage LiNi0.5Mn1.5O4 Cathode via the Sculpture Method toward Enhanced Stability.

High-voltage LiNi0.5Mn1.5O4 (LNMO) cathodes suffer from severe capacity degradation during long-term cycling due the manganese dissolution and their high operating voltage (∼4.95 V), which pose serious challenges at the surface or interface. Moreover, both traditional ion-doping and passivation layer coating are difficult to apply consistently to LNMO cathode because of their complicated procedures, especially in large-scale production. To address these issues, a strategy employing HNO3/H2O2 leaching in synergy with a sintering process at a mid-temperature of 700 °C was used to achieve selective surface reconstruction. An optimal ratio of reactants was applied to balance the capacity and the cyclic stability of the LNMO cathode. The optimized valence composition of Mn on the material surface mitigates the occurrence of Jahn-Teller distortion, accompanied by a reasonable ratio of ordered and disordered phases and the concentration of oxygen vacancies after sintering, which improves the interface behavior between the electrode and electrolyte. This method delivers a high reversible capacity of 116.5 mAh g-1 after 200 cycles at 0.5 C (1 C = 147 mAh g-1) with a capacity retention of 91.30% and 110 mAh g-1 with a remarkably high capacity retention of 86.85% after 500 cycles at 2 C. This balanced approach, utilizing the protective effects of oxidation (O22-) and the erosive action of acid (H+), is proposed to achieve regional surface reconstruction of advanced LNMO cathode. This opens up a strategy for improving oxide-based cathode materials with low cost and mass production capability, especially favoring high consistency.

Construction of more oxygen vacancies of BaCo0.4Fe0.4Zr0.2O3-δ for high-performance proton-conducting solid oxide fuel cell cathodes

The cathodic catalytic activity for the oxygen reduction reaction (ORR) plays a critical role in determining the performance of proton-conducting solid oxide fuel cells (P-SOFCs). BaCo0.4Fe0.4Zr0.2O3-δ (BCFZ) has emerged as a promising cathode for P-SOFCs due to its triple-phase conductivity. Nevertheless, its suboptimal proton conductivity and hydration ability at intermediate temperatures prevent it from achieving the anticipated ORR catalytic activity. To address these limitations, this study explores the enhancement of electrocatalytic activity in BCFZ through alkali metal doping and A-site defect construction. The effects of such modifications on oxygen surface exchange kinetics and ORR catalytic activity are systematically investigated. The findings reveal that BCFZ exhibits relatively low parameters in terms of electronic conductivity, oxygen ion conductivity, oxygen vacancy concentration, kchem, and Dchem. Conversely, these parameters are markedly improved in A-site deficient BCFZ (D-BCFZ) and Na/K-doped BCFZ. Consequently, the enhancement of these properties yields a significant increase in ORR catalytic activity, with D-BCFZ demonstrating the best electrochemical performance. Specifically, P-SOFC with D-BCFZ cathode achieves an Rp value of just 0.073 Ω cm2 and a Pmax value of 0.928 W cm−2 at 650 °C. This study provides theoretical insight into the mechanisms by how alkali metal doping and defect construction enhance the ORR catalytic activity of BCFZ. These findings offer valuable guidance for the development and optimization of high-performance P-SOFC cathodes.

Generation of oxygen vacancies in CuO/TiO2 heterojunction induced by diatomite for highly efficient UV–Vis-IR driven photothermal catalytic oxidation of HCHO

Photothermal catalytic oxidation is a promising and sustainable method for the degradation of indoor formaldehyde (HCHO). However, the excessively high surface temperature of existing photothermal catalysts during catalysis hinders the effective adsorption and degradation of formaldehyde under static conditions. Catalyst loading and oxygen vacancies (OVs) modulation are commonly employed strategies to reduce the photothermal catalytic temperature and enhance the efficiency of photothermal catalytic oxidation. In this work, a p-n type CuO/TiO2 heterojunction is successfully loaded onto diatomite using a wet precipitation method. Under the irradiation of a 300W xenon lamp, the prepared composite material achieved a 100% removal rate of HCHO within 2 h, with a 98% conversion rate to CO2, surpassing the performance of both individual photocatalysts and thermocatalysts. Additionally, by adjusting conditions such as light irradiation and temperature, we have demonstrated that this material exhibits synergistic photothermal catalytic properties. Based on HRTEM, XPS, Raman, and EPR analyses, the introduction of diatomite as a catalyst support was shown to effectively increase the number of OVs. Experimental results, along with O2-TPD, photoelectrochemical characterization, and radical detection, demonstrate that the presence of OVs enhances the oxidative efficiency of both photocatalysis and thermocatalysis, as well as the UV–Vis-IR photothermal catalytic performance. The ternary composite material generates weak hydroxyl (•OH) and superoxide (•O2−) radical under high-temperature with dark conditions, indicating its catalytic oxidation activity under this condition. The increase in temperature and the expansion of the spectral range both enhance the generation of these radicals. In summary, this work demonstrates that the use of diatomite as a support increases the material's specific surface area and OVs content, thereby enhancing adsorption and photothermal catalysis. It elucidates the enhanced catalytic degradation mechanism of this mineral-based photothermal catalyst.

Study on the homologous effects on the performance of alkali metal-doping MgO-based adsorbents for CO2 capture

In this article, MgO-based adsorbents with different structure and surface property were prepared by combustion of the colloids containing Mg and alkali metal. At the same time, CO2 adsorption performance tests are conducted to compare the doping effect of alkali metal on MgO adsorbents. As confirmed, the introduction of lithium, sodium, and potassium can reduce the grain size of MgO and enhance the basicity, especially increasing the concentration of oxygen vacancies on MgO surface which exposed more basic adsorption active sites and was more conducive to CO2 adsorption. Among them, the one doped with 0.5 % K which had more electron shell numbers showed larger surface area and smaller crystal size. Most importantly, it provided more number of basic sites along with the improved strength of surface basicity due to the more oxygen vacancies. As a result, the maximum CO2 uptake (1.09 mmol/g) at the adsorption time of 60 min can be obtained which still remained at 0.67 mmol/g after 16 cycles of CO2 adsorption–desorption. With the aid of N2 physical adsorption, inductively coupled plasma-optical emission spectroscopy, powder X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and chemical adsorption, the relationship between CO2 adsorption capacity of MgO-based adsorbent and homologous regularity of alkali metal was disclosed. In other words, by comparing the CO2 adsorption performance of MgO adsorbents prepared by doping different alkali metals, CO2 adsorption capacity increased with the increase of electron shell numbers. Such a configuration is in favor of the electron supply of the p-orbitals and weakens the Mg–O bonds which promoted the formation of oxygen vacancies. The found will provide in-depth understanding for the modification and performance improvement of MgO-based adsorbents.

In-situ constructing oxygen-enriched vacancies BiOCl with 3D flower-structure for exceptional visible-light-driven photocatalytic properties

Bismuth oxychloride (BiOCl), emerging as a novel environmentally friendly nanomaterial, possesses considerable potential for photocatalytic degradation of organic wastewater. However, inadequate active sites and inhibited electron separation efficiency severely hinder its visible-light photocatalytic activity. To address this issue, herein we present a facile approach to in-situ construct BiOCl three-dimensional (3D) flower-structure (BOC-F) with oxygen-enriched vacancies for abundant active sites and effective electron separation efficiency through morphology control and vacancy engineering. The visible photocatalytic activity of BOC-F and BiOCl with 2D flaky-structure (BOC-S) was assessed through a systematic examination of the degradation efficiencies of tetracycline hydrochloride (TC-HCl) and rhodamine B (RhB). Under visible light irradiation, BOC-F exhibited superior visible photocatalytic activity, effectively degrading tetracycline hydrochloride (TC-HCl) (20 mg/L) and rhodamine B (RhB) (200 mg/L) within 90 min and 20 min of light exposure, respectively. The findings elucidate that BOC-F, possessing a 3D flower structure, manifests a heightened concentration of oxygen vacancies in contrast to BOC-S, consequently yielding excellent performance. Moreover, The ESR test showed that singlet oxygen (1O2) and hole (h+) were two main active species in the photocatalytic degradation of BOC-F. This work not only furnishes a facile method for constructing oxygen-rich vacancies in BiOCl but also provides fresh insights into the potential for enhancing the visible photocatalytic properties of Bi-based materials through vacancy engineering.

Optimizing Reversible Exsolution and Phase Transformation in Double Perovskite Sr2Fe1.5-xCoxMo0.5O6-δ Electrodes for High-Performance Symmetric Solid Oxide Cells.

Double perovskite (DP) oxides are promising electrode materials for symmetric solid oxide cells (SSOCs) due to their excellent electrochemical activity and stability. B-site cation doping in DP oxides affects the reversibility ofphase transformation and exsolution, which plays a crucial role in the catalyst recovery. Yet, few studies have been conducted on this topic. In this study, the Sr2Fe1.5-xCoxMo0.5O6-δ (CSFM, x = 0, 0.1, 0.3, 0.5) DP system demonstrates modulated exsolution and phase transformation reversibility by manipulating the oxygen vacancy concentration. The correlation between Co-doping level and oxygen vacancy concentration is investigated to optimize the exsolution and phase transformation properties. Sr2Fe1.2Co0.3Mo0.5O6-δ (3CSFM) exhibits reversible transformation between DP and Ruddlesden-Popper phases with a high density of exsolved CoFe nanoparticles under redox atmospheres. The quasi-symmetric cell with 3CSFM shows a peak power density of 1.27Wcm-2 at 850°C in H2 fuel cell mode and a current density of 2.33Acm-2 at 1.6V and 800°C in H2O electrolysis mode. The 3CSFM electrode exhibits robust stability during continuous operation for ≈700h. These results demonstrate the significant role of B-site doping in designing DP materials capable of dynamic phase transformation in diverse environments.

Study on Ce-MOF-derived oxides as morphology-tunable catalyst supports for dry reforming of methane

Dry reforming of methane (DRM) using CH4 and CO2 as feedstocks to catalytically produce high-value synthesis gas products has great application prospects. However, as a high-temperature heterogeneous catalytic reaction, the challenge lies in preparing efficient and stable catalysts for long-term operation. To enhance the catalytic performance by optimizing support, this study proposed regulating the catalyst structure and properties using Ce-based metal-organic framework (MOF) derivatives. Compared with the conventional Ni/CeO2, Ni/CeO2-MOF catalysts performed better in DRM. Especially, Ni/CeO2-UiO-66 demonstrated significant improvement in both catalytic activity and stability. It was also noticed that the Ni/CeO2-MOF catalysts had a potential benefit in limiting the conversion of carbon species to inactive forms given the relatively lower carbon gasification temperatures at their surfaces. The advantage of Ni/CeO2-MOF catalysts was attributed to their better void structure and reduction characteristics, as well as higher oxygen vacancy concentration and improved CO2 adsorption activation capability after pre-activation. This study revealed that MOF-derived supports had distinctive structural characteristics, which were manifested as an important component in high-temperature catalyst systems.

Zn-based and Al-based MOF photocatalysts with abundant oxygen vacancies for fixing nitrogen effectively under mild conditions

Photocatalytic nitrogen fixation is an environmentally friendly process for turning atmospheric nitrogen into ammonia under mild conditions. In this study, MOF photocatalysts Zn-bpydc and Al-bpydc with good nitrogen fixation effect were prepared by a simple one-pot method. The rates of ammonia generation for Zn-bpydc and Al-bpydc at normal temperature and pressure were 796.1 µg g-1 h−1 and 684.0 µg g-1 h−1, respectively. The ESR test demonstrated that Zn-bpydc exhibits a higher concentration of oxygen vacancies than Al-bpydc, allowing it to chemically adsorb N2 and construct an effective electron transport pathway, hence enhancing the catalyst’s photocatalytic activity. This study provides a simple, efficient and economical MOF photocatalysts that can contribute to sustainable development.

Oxygen Vacancy Controlled Hyperbolic Metamaterial Based on Indium Tin Oxide (ITO) Nanotubes with Switchable Optical Properties

AbstractNanostructured metamaterials can offer optical properties beyond what is achievable in conventional media, such as negative refraction or sub‐wavelength imaging. Due to their structural anisotropy, the class of high aspect ratio metamaterials is of interest for the possibility of achieving hyperbolic optical properties, i.e., both metallic and dielectric behavior based on the excitation direction. Although investigated numerically, the fabrication of tailor‐made metamaterials is complex or often beyond the reach of current technology. For wire metamaterials composed of aligned metallic nanowires in a dielectric matrix, since the free carrier concentration in metals is fixed, light‐matter interaction cannot be adjusted after fabrication. Here, metamaterials based on plasmonic ITO nanotubes with controllable hyperbolic response are introduced. The synthesis is achieved by a template‐based liquid‐phase technique. The tuning mechanism is based on controlling the carrier density in ITO via oxygen vacancy concentration. The process is reversible, the photonic features are activated by creating oxygen vacancies and can be switched off by filling them up again. Further, it is shown that the carrier concentration can also be controlled via a static electric field. Optical simulations support the experimental findings and highlight the parameters that determine the optical response of the metamaterial.