Creation Of Oxygen Vacancies Research Articles

The Activation of Oxygen Species on the Pt/CeO2 Catalyst by H2 for NO Oxidation

The Pt/CeO2 catalyst has attracted significant attention due to its exceptional performance in NO oxidation. This study comprehensively examines the effects of calcination temperature and H2 pretreatment on the structure and activity of the Pt/CeO2 catalyst. Experimental findings indicate that the calcination temperature significantly affects the catalyst’s redox performance, thereby modulating its efficacy in NO oxidation reactions. H2 pretreatment facilitates the creation of oxygen vacancies on the catalyst, assisted by the reduction in PtOx to Pt, enhancing the formation of activated oxygen and thereby improving NO oxidation. This study offers valuable insights into the design and optimization of Pt/CeO2 catalysts for environmental applications, particularly in the development of exhaust gas after-treatment technologies.

Deciphering the Ce3+to Ce4+Evolution: Insight from X-ray Raman Scattering Spectroscopy at Ce N4,5Edges.

Cerium oxide, or ceria, (CeO2) is one of the most studied materials for its wide range of applications in heterogeneous catalysis and energy conversion technologies. The key feature of ceria is the remarkable oxygen storage capacity linked to the switch between Ce4+ and Ce3+ states, in turn creating oxygen vacancies. Changes in the electronic structure occur with oxygen removal from the lattice. Accordingly, the two valence electrons can be accommodated by the reduction of support cations where the electrons can be localized in empty f states of Ce4+ ions nearby.Quantifying the different oxidation states in situ is crucial to understand and model the reaction mechanism. Beside the different techniques to quantify Ce3+ and Ce4+ states, we discuss the use of X-ray Raman Scattering (XRS) spectroscopy as an alternative method. In particular, we show that XRS can observe the oxidation state changes of cerium directly in the bulk of the materials under realistic environmental conditions. The Hilbert++ code is used to simulate the XRS spectra and quantify accurately the Ce3+ and Ce4+ content. These results are compared to those obtained from in situ X-ray Diffraction (XRD) collected in parallel and the differences arising from the two different probes are discussed.

Recent Advances in Electronic Structure Modifications of Layered Double Hydroxide (LDH) for the Water Splitting Application

AbstractElectrocatalytic water splitting is a feasible method for large‐scale hydrogen production. Recently, layered double hydroxides (LDH) have been identified as a possible candidate for accelerating the water splitting process. Nevertheless, certain structural alterations are necessary for immaculate LDH because of their weak electrocatalytic activity. These structural changes alter the local reaction environment by modulating the electronic structure of the metal center present in the LDH. This electronic structure tailoring is accomplished by a variety of processes, including heteroatom doping, single atom inclusion, cationic defect, oxygen vacancy creation, and heterostructure formation. Recently, there has been an uptick of advancement in this field, and it is necessary to summarize these developments. This review provides a concise summary of the current reports on the electronic structure manipulation of layered double hydroxide. The review begins by examining the local environmental changes of LDH resulting from the insertion of single atoms. Subsequently, we explore the charge transfer that occurs at the interface between LDH and other transition metal heterostructures. In addition, we explored the impact on the metal center near the vacancies on the basal plane of LDH. Finally, we presented a future perspective and guidance for advancing this field in electrocatalysis.

Cation rearrangement at tetrahedral sites in the Cu/ZnAl2O4 spinel enhancing CO2 hydrogenation to methanol

Cu/ZnAl2O4 spinel is a promising catalyst for CO2-to-methanol due to its dual-site H2 activation. However, controlling surface properties and metal-support interactions (MSI) through the coordination environment of spinel cations remains underexplored. Herein, the occupancy of Zn2+ and Al3+ cations in Cu/ZnAl2O4 spinel is fine-tuned by manipulating the calcination atmosphere. More disordered structures (AlO4 and ZnO6) observed on the CZA-Ar catalyst benefit the creation of oxygen vacancies and surface hydroxyl groups, which facilitate the formation of highly dispersed small-sized Cu species. This enhances MSI and hydrogen spillover effects, thereby boosting CO2 conversion and the space-time yield (STY) of methanol. High-pressure in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that the crucial formate intermediates form at tetrahedral sites in ZnAl2O4 spinel, with more Al-HCOO- species observed on the CZA-Ar catalyst due to the formation of AlO4. This work advances the understanding of spinel catalysts in CO2 hydrogenation to methanol.

Modification of solar energy and photoelectrochemical water splitting properties: using FTO/Er-TiO2/MAPbI3/CuPc/Au as modified photoelectrode

In the past decades, converting solar energy into hydrogen through photoelectrochemical water splitting has been attracted. Here, we designed a new FTO/Er-TiO2/MAPbI3/CuPc/Au photoanode with n-i-p structure for using in solar water splitting. Accourding to obtained PEC results, the FTO/Er-TiO2/MAPbI3/CuPc/Au photoanode has a photocurrent density of ∼9.8 mA cm−2 ( under a visible lamp with intensity of 100 mW cm−2 irradiation) compared to FTO/Er-TiO2/Au and FTO/Er-TiO2/MAPbI3/Au photoanodes with photocurrent density of 0.7 and 6.12 mA cm−2, respectively. This important enhancement is refered to the light absorption feature of Er-TiO2/MAPbI3 and a fast electron and hole transfer process in the Er-TiO2 and CuPc, respectively. The photoelectrochemical action of the photoelectrode is increased using erbium doping due to creation of oxygen vacancies and titanium (III) ions. Furthermore, in this research, we studided the power conversion efficiency (PCE) of FTO/Er-TiO2/MAPbI3/Au and FTO/Er-TiO2/MAPbI3/CuPc/Au solar cells. The results shown that the significant enhancement in photovoltaic properties can be observed by utilizing spin-coated CuPc nanoparticles (as hole transport layer) at least by 1.39% compared to the FTO/Er-TiO2/MAPbI3 perovskite solar cell.

Synergy of the heterojunction and defects engineering in Zr-doped TbFeO3@g-C3N4 photo-nanocatalyst towards enhanced visible-light-driven antibiotics degradation and H2 production

Environmental remediation and energy production are major concerns of the globe for sustainable development. Solar-driven photo nanocatalysts have shown great potential to be a suitable contender to solve these issues, however, their catalytic efficiency is the major concern which depends on the e−/h+ pair separation. The present study developed TbFe0.95Zr0.05O3/g-C3N4 heterostructure employing facile hydrothermal methods to promote e−/h+ pair separation. Though, TbFe0.95Zr0.05O3/g-C3N4 achieved the highest photo-degradation of 95.96 % for Norfloxacin (NOR) in 90 min, and 4864 μmol h−1g−1 of H2 evolution in 4 h under simulated visible-light, with 3.3, 2.8 and 2.1 times higher efficiency than pristine and doped catalysts (TbFeO3, g-C3N4 and TbFe0.95Zr0.05O3). The creation of oxygen vacancies (OVs) by Zr4+ doping at Fe3+ sites through charge compensation may increase catalytic efficiency, confirmed through X-ray photoelectron spectroscopy (XPS), and optical properties through Raman, and photoluminescence spectroscopy (PL). The catalyst works well throughout four cycles (85.19 % for NOR in the 4th cycle), demonstrating its chemical stability and cyclic potential. Thus, heterojunction and OVs synergistically enhance catalytic efficiency with higher activation in the visible solar spectrum and long e−/h+ charge separation lifetime.

A techno-economic and environmental evaluation of the integration of direct air capture with hydrogen derivatives production

Carbon-neutral fuels are key to decarbonizing hard-to-abate sectors. Solar redox cycles can produce them by creating oxygen vacancies in a metal oxide capable of splitting water and CO2. The resulting synthesis gas can be processed into a liquid fuel like methanol. To close the carbon cycle, feedstock CO2 can be captured from the atmosphere with direct air capture (DAC), but the synergies between synthetic fuel production and DAC are largely unexplored. In this work, four integration strategies between DAC and solar redox cycles are proposed. Each of them is modeled with Aspen Plus and HFLCAL and compared with a techno-economic and a cradle-to-gate life cycle assessment. The optimal configuration, with a levelized cost of 7.9 ± 0.4 USD2022/kgMethanol and a climate change impact of −450 ± 30 g CO2e/kgMethanol, uses solid DAC powered by waste heat. Therefore, the study recommends the integration of DAC in the production of synthetic fuels.

Green mediated sol-gel synthesis of MxCu1-xO (M = La,Ce x = 0.02–0.06) as an efficient catalyst for electrocatalytic oxygen evolution reaction

The imperative for advancing contemporary human society lies in the essential requirement to create energy generation systems that are sustainable, environmentally friendly, and exceptionally efficient. The development of efficient electrocatalysts, that are environmentally benign, economically viable and easily available, for alkaline oxygen evolution reaction is a significant research area in this regard. The present study focuses on a green mediated sol–gel auto-combustion process for the synthesis of lanthanum and cerium doped copper oxide nanoparticles with excellent electrocatalytic activity. Citric acid and polyols enriched lemon juice serves as the medium for the synthesis of various metal doped copper oxide nanoparticles. The extensive electrochemical studies using these catalysts reveals that, among the various doped samples, 5% lanthanum and 5% cerium doped catalysts exhibited the best performance in oxygen evolution reaction. Doping was found to enhance electrical conductivity and create oxygen vacancies, which enhanced the electrocatalytic activity of the catalysts. Specifically, the 5% lanthanum-doped copper oxide showed an overpotential of 340 mV, while the cerium-doped material exhibited an overpotential of 337 mV at a current density of 10 mA cm−2 in 1 M KOH. Moreover, the lanthanum-doped sample displayed a Tafel slope of 49 mV dec−1, whereas the cerium-doped sample had a Tafel slope of 60 mV dec−1 with better durability. Additionally, the chronopotentiometric studies revels the stability and long-term performance of LCO5 and CCO5, maintaining consistent potential of 1.58 V throughout 5 h at a current density of 10 mA cm−2. This study is conclusive evidence that the incorporation of rare earth elements improves the conductivity and overpotential of pristine copper oxide nanoparticles, making them highly effective in the oxygen evolution reactions.

Renewable Diesel Production over Mo-Ni Catalysts Supported on Silica

Nickel catalysts promoted with Mo and supported on silica were studied for renewable diesel production from triglyceride biomass, through the selective deoxygenation process. The catalysts were prepared by wet co-impregnation of the SiO2 with different Ni/(Ni + Mo) atomic ratios (0/0.84/0.91/0.95/0.98/1) and a total metal content equal to 50%. They were characterized by XRD, XPS, N2 physisorption, H2-TPR, and NH3-TPD. Evaluation of the catalysts for the transformation of sunflower oil to renewable (green) diesel took place in a high-pressure semi-batch reactor, under solvent-free conditions. A very small addition of Mo, namely the synergistic Ni/(Ni + Mo) atomic ratio equal to 0.95, proved to be the optimum one for a significant enhancement of the catalytic performance of the metallic Ni/SiO2 catalyst, achieving 98 wt.% renewable diesel production. This promoting action of Mo has been attributed to the significant increase of the metallic Ni active phase surface area, the suitable regulation of surface acidity, the acceleration of the hydro-deoxygenation pathway (HDO), the creation of surface oxygen vacancies, and the diminution of coke formation provoked by Mo addition.

Poly(3,4-ethylenedioxythiophene)-Coated Vanadium-Doped MnO2 Nanorods for High-Performance Flexible Aqueous Zinc-Ion Battery Cathode.

Manganese-based aqueous zinc-ion batteries (AZIBs) are considered promising cathode materials for large-scale energy storage applications due to their low cost and high safety. However, the primary constraints on achieving high specific capacity and cycling stability are the inherent low conductivity and suboptimal structural stability of the AZIB cathodes. Herein, we report a high-performance poly(3,4-ethylenedioxythiophene) (PEDOT)-coated vanadium-doped MnO2 nanorod (NR) electrode for AZIBs. First, vanadium-doped MnO2 (V-MnO2) NRs were synthesized by a simple hydrothermal synthesis method. The V-MnO2 NRs were further encapsulated with a nanolayer of PEDOT through an in situ polymerization process, which was subsequently treated with sulfuric acid to achieve a smooth surface. The V doping creates oxygen vacancies within the MnO2, allowing for the rapid embedding and diffusion of Zn2+. The PEDOT nanolayer greatly enhances the conductivity and structural stability of the V-MnO2. Benefiting from the unique features, an optimal composite NRs electrode exhibits a high specific capacity of 250 mAh g-1 at 0.4 A g-1, a high energy density (388 Wh kg-1 at 151 W kg-1), and excellent stability over 5000 cycles at 3 A g-1. In addition, the flexible pouch cell assembled with the electrode shows good stability under bending. Given the positive outcomes, the material holds great potential for use as a cathode in next-generation flexible energy storage systems.

Low-pressure CO2 hydrogenation coupled with toluene methylation to para-xylene using atomic Pd-doped ZnZrOx–HZSM-5

Selective methylation of aromatics using CO2/H2 presents a promising avenue for producing high-value-added chemicals with high selectivity. Herein, we introduced atomically dispersed Pd species into ZnZrOx solid solution and combined with HZSM-5 to create a bifunctional catalyst, applying to selectively synthesize para-xylene through toluene methylation using CO2/H2 at low pressure. Remarkably, 0.1 wt% Pd in PdZnZrOx–HZSM-5 afforded the selectivity of xylene in CO-free products and para-xylene in xylene to 90.0% and 85.6% at 0.5 MPa, respectively. Spectroscopic characterizations revealed that atomically dispersed Pd species enhance the dissociation of adsorbed hydrogen and facilitate the creation of oxygen vacancies, benefiting the CO2 hydrogenation to CHxO intermediates. Density functional theory calculations suggested that Pd-doped ZnZrOx reduces the energy barrier for hydrogenating H2COOH* to H2CO*, aiding to form CH3O* intermediate for toluene methylation. This work provides insights into the design of catalysts for the selective methylation of aromatics using CO2/H2 at low pressure.

High-quality femtosecond laser cutting of battery electrodes with enhanced electrochemical performance by regulating the taper angle: Promoting green manufacturing and chemistry

Laser cutting electrode technology is an environmentally friendly and sustainable manufacturing method that offers many benefits, such as low energy consumption and greenhouse gases, no waste production, no tool wear, flexible manipulation, and multi-scale processing. However, achieving high cutting quality with adjustable notch shape and controllable dimension precision is still a cutting-edge challenge. In addition, the influence of laser cutting on the microscopic structure and electrochemical performance of battery electrodes has not been fully illustrated. Here, the Li4Ti5O12 (LTO) electrode is cut using a femtosecond laser technology. The processing parameters are systematically optimized, and the influence of laser cutting taper structure on the structure and performance of LTO electrodes is comprehensively investigated. It is found that laser photoionization and the generated plasma could create oxygen vacancies and thus more Ti3+/Ti4+ defects in the LTO electrodes, resulting in increased electronic conductivity. Moreover, proper taper structure could help improve electrolyte infiltration as well as Li+ diffusion kinetics. As a result, the laser cutting LTO electrode with the optimized taper angle of T = 0.004 shows excellent electrochemical performance. The capacity retention is more than 99.2 % after 400 cycles at 1C, and the specific capacity reaches ∼60 mAh g−1 at a high rate of 60C, which is about 1.7 times higher than that of mechanically cutting LTO electrodes. The outstanding electrochemical performance is also demonstrated by LiFePO4||Li4Ti5O12 full cells. This work could pave the way for the development and application of laser technology in cutting battery electrodes.

Atomic Defects Engineering Boosts Urea Synthesis toward Carbon Dioxide and Nitrate Coelectroreduction.

The atomic defect engineering could feasibly decorate the chemical behaviors of reaction intermediates to regulate catalytic performance. Herein, we created oxygen vacancies on the surface of In(OH)3 nanobelts for efficient urea electrosynthesis. When the oxygen vacancies were constructed on the surface of the In(OH)3 nanobelts, the faradaic efficiency for urea reached 80.1%, which is 2.9 times higher than that (20.7%) of the pristine In(OH)3 nanobelts. At -0.8 V versus reversible hydrogen electrode, In(OH)3 nanobelts with abundant oxygen vacancies exhibited partial current density for urea of -18.8 mA cm-2. Such a value represents the highest activity for urea electrosynthesis among recent reports. Density functional theory calculations suggested that the unsaturated In sites adjacent to oxygen defects helped to optimize the adsorbed configurations of key intermediates, promoting both the C-N coupling and the activation of the adsorbed CO2NH2 intermediate. In-situ spectroscopy measurements further validated the promotional effect of the oxygen vacancies on urea electrosynthesis.

N-doped carbon dots-modulated interfacial charge transfer and surface structure in FeNbO4 photocatalysts for enhanced CO2 conversion selectivity to CH4

The photocatalytic carbon dioxide reduction reaction (CO2RR) is an innovative and reliable technology to address the issues of energy shortage and climate change simultaneously. However, issues such as insufficient light absorption, rapid electron-hole recombination and low surface activity during CO2RR severely limit the catalysts’ efficiency for photocatalysis. In this study, we present nanohybrid N-CDs/FeNbO4 catalysts to overcome these challenges and achieve high-efficient photocatalytic conversion of CO2 to CH4. The enhancement process starts with the introduction of modified N-CDs, which have a broad light absorption capability. These N-CDs also help to modulate the interfacial charge transfer kinetics, leading to improved charge separation and transfer. This, in turn, enhances the multielectron transfer conversion selectivity of CO2 to CH4. Meanwhile, CO2 adsorption on the photocatalysts is increased due to the creation of oxygen vacancies and lattice stresses resulting from the introduction of N-CDs. This work presents a new approach for improving the photocatalytic performance by adjusting surface structure and interfacial behaviors.

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.

Exploring electrochemical kinetic behaviors and interfacial charge transfer of pure and Ni-doped ZnFe2O4 nanoparticles-based sensing nanoplatform for ultra-sensitive detection of chloramphenicol

ZnFe2O4 (ZFO) nanomaterial was doped with a divalent transition metal cation of Ni2+ (NixZn1-xFe2O4, x=0, 0.2, 0.4, and 0.8) and characterized by various analytical techniques. Powder X-ray diffraction revealed the formation of a single-phase cubic spinel structure, while the stabilization of crystal structure for Ni2+-doped samples was observed. The average crystalline size, d-spacing, and lattice parameters increased with increasing in Ni2+ concentration within NixZn1-xFe2O4, due to differences in the ionic radius, the cation distribution at A-B sites, and the creation of surface oxygen vacancies within ZFO structure. From electrochemical measurements, NixZn1-xFe2O4-based electrodes showed excellent enhancements in charge transfer ability and conductivity with the highest rate constant (0.018 ms−1), the lowest peak-to-peak separation (206 mV), the lowest Rct (118 Ω), and the largest electrochemical active area (0.248 cm2), compared to that of bare SPE. Among them, Ni0.8Zn0.2Fe2O4/SPE provided outstanding electrochemical behaviors and achieved the best sensing performance with the widened concentration linear range from 0.25 to 50 μM and a rather low detection limit of 0.2 μM for chloramphenicol detection. The most important reason for this positive advance comes from the unique synergistic effects of Ni doping into the ZFO host structure. The excellent enhancements in adsorption capacity (Г) (1.4 times higher), number of oxygen vacancies, charge transfer rate constant (approximately 1.15 times higher), and catalytic rate constant (30 times greater) were recorded at Ni-doped ZFO-based electrodes, compared to pure ZFO-based electrode. Furthermore, the detailed hypotheses and possible mechanisms explaining these impressive enhancements were explored. Our work provides insight into the correlation between the Ni-doping and electrochemical characteristics, which has implications for tailoring the electrochemical performance of spinel ferrites across diverse applications and the design of novel spinel ferrite nanomaterials.

Microstructure and thermoelectric properties of non-equimolar high-entropy [Ca(1-x)/3Sr(1-x)/3Ba(1-x)/3Lax]TiO3 perovskite ceramics

Entropy engineering has emerged as an important means of optimizing the properties of SrTiO3-based thermoelectric materials. However, the relationship between configurational entropy and thermoelectric properties is currently unclear. In this work, non-equimolar high-entropy thermoelectric ceramics [Ca(1-x)/3Sr(1-x)/3Ba(1-x)/3Lax]TiO3 (0.10 ≤ x ≤ 0.40) were prepared by spark plasma sintering. And the effects of composition and configurational entropy on the microstructure and thermoelectric properties of the materials were investigated. It is revealed that high entropy effect profoundly modified the microstructure of the material. The grain size decreases with increasing configurational entropy, the interaction of multiple cations leads to lattice distortions, and the sintering and annealing process induces the creation of oxygen vacancies, which significantly affect thermoelectric properties. The highest ZT (0.20) was obtained at a lanthanum content of 0.19 (ΔSConf=11.483 J/mol/K). This work provides theoretical and experimental bases for optimizing the thermoelectric properties of the materials by using high entropy design.

Modulating Carrier Oxygen Vacancies to Enhance Strong Oxide‐Support Interaction in IrO2/Nb2O5‐x Catalysts for Promoting Acidic Oxygen Evolution Reaction

AbstractGiven the pronounced dissolution of electrocatalysts in acidic environments, the quest for effective oxygen evolution reaction (OER) electrocatalysts suitable for proton exchange membrane (PEM) water electrolyzers persists as a formidable challenge. In this investigation, catalysts are synthesized by creating oxygen vacancies within various metal oxides (Nb2O5‐x, Ta2O5‐x, ZrO2‐x, TiO2‐x) through plasma‐assisted method, thereby facilitating the immobilization of IrO2 onto these defect‐rich surfaces. The findings unveil that IrO2/Nb2O5‐x manifests reduced overpotentials during acidic OER, achieving an overpotential down to 225 mV@10 mA cm−2, coupled with outstanding durability at multicurrent densities exceeding 200 h, attributed to strong oxide‐support interaction (SOSI) between the IrO2 catalyst and Nb2O5‐x substrate. Density functional theory (DFT) computations uncover intensified binding affinities between IrO2 and Nb2O5‐x, thus modulating the central energy levels of Ir's d orbitals toward favorable OER conditions, consequently bolstering the electrocatalytic activity and stability of the composite catalyst. Furthermore, employing IrO2/Nb2O5‐x as a PEM electrolyzer anode enables consistent operation at 1000 mA cm−2 for 200 h, with an Ir content of only 0.2852 mg cm−2 and an energy consumption of 4.34 kWh Nm−3 H2. This achievement substantially lowers the cost of hydrogen production to US$ 0.96 per kilogram, underscoring its potential for practical applications.

Noble metal-free plasmonic Cu/WO3-x@ZNC bi-functional composite for ciprofloxacin photocatalytic degradation and photothermal water evaporation via visible-infrared exposure

Herein, coupling of noble metal-free plasmonic copper nanoparticles with tungsten suboxide and supporting on zeolite nanoclay (Cu/WO3-x@ZNC) composite will be introduced for bi-functional photocatalytic ciprofloxacin (CIP) degradation and water photothermal evaporation under visible/infrared (Vis/IR) exposure. Reduced band-gap of WO3-x via oxygen vacancies creation and localized surface plasmon resonance (LSPR) formation by Cu nanoparticles contributed significantly the extension and intensification of composite's photo-absorption range. Furthermore, small mesoporous structure of ZNC enhanced CIP adsorption and charge carriers separation where the reported photocatalytic efficiencies were 88.3 and 81.7% upon IR and Vis light exposure respectively. It was evidenced that plasmonic hot electrons (e−.s) and hydroxyl radicals (OH•-) performed the basic functions of the photocatalytic process. At the other side, oxygen vacancies existence, plasmonic effect, and confining thermal characteristics of WO3-x, Cu, and ZNC correspondingly induced water photothermal evaporation with efficiencies up to 97.5 and 72.8% under IR and Vis illumination respectively. This work introduces synthesis of a novel bi-functional photocatalytic-photothermal composite by metal sub-oxide and non-noble metal plasmonic coupling and supporting on naturally-derived carrier for water restoration under broad spectral exposure.

Copper-perovskite interfacial engineering to boost deNOx activity

By adjusting the Cu doping level and calcination temperature during synthesis of a series of noble metal-free lanthanum copper manganite perovskites LaCuxMn1-xO3, we show the importance of tuning the redox chemistry for optimum steering of the catalytic activity and N2 selectivity in the catalytic reduction of NO by CO. A prerequisite is the in situ formation of an extended copper-perovskite phase boundary. The associated improvement of redox and surface properties by Cu addition leads to an optimized balance of the reduction of the catalyst in the NO+CO reaction mixture. The creation of oxygen vacancies improves the reaction kinetics and initiates the NO dissociation. Strongly dependent on the calcination temperature, the Cu/Mn ratio, the reducing agent, as well as the reaction temperature as parameters for Cu-perovskite interfacial control, surface reduction can induce partial copper exsolution, significant perovskite reduction, agglomeration of exsolved Cu particles and eventual decomposition of the catalyst structure. We show that increasing the amount of initial copper incorporated into the perovskite structure can beneficially extend the phase boundary, but exceeding the amount of copper leads to increased sintering of the copper particles at the expense of catalyst activity, especially in repeated catalytic cycles. Increasing the calcination temperature, in addition to the initial sintering of the catalyst and shifting the reaction onset temperature to higher temperatures in the first cycle, improves the reduction resistance of the catalyst. Consequently, in order to form a higher amount of phase boundary-bound active sites, stronger reducing conditions than provided by the NO+CO reaction mixture are needed. This effect can be counterbalanced by using stronger reduction agents prior to performing subsequent catalytic cycles by inducing the exsolution process.