Oxide Research Articles

Advances in deep eutectic Solvent-Based synthesis of nanomaterials for environmental remediation

The application of eco-friendly deep eutectic solvents (DES) in the functionalization and synthesis of adsorbent materials has gained significant research interest in recent times. These materials, employed for treating polluted water primarily through degradation or adsorption, are emerging as sustainable alternatives to traditional technologies. However, the information regarding the functionalization and synthesis of adsorbent materials using DES is dispersed throughout the literature. This review aims to consolidate and clarify the extensive information available on the synthesis and functionalization of DES-based adsorbents, their application in water treatment as nanomaterials, and the future prospects of such technologies. DES presents an ideal alternative to conventional solvents for modifying and functionalizing adsorbents due to their lower toxicity, cost-effectiveness, and environmental friendliness. Most DESs effectively introduce desired functionalities and enhance the surface area of adsorbents, thereby greatly enhancing the removal of pollutants. This review compiles recent literature on the synthesis and modification of graphene oxides, carbon nanotubes, metal oxides, and other materials for the degradation/adsorption of pharmaceuticals, herbicides, dyes, pesticides, heavy metal ions, and other water contaminants. Besides this, DES-based nanomaterials have potential future applications in nanotechnology, nanofluids, nanocatalysts, biosensors, environmental remediation, among others. The anticipated exponential growth in these areas underscores the urgent need for such a review.

Prospect for recycling critical elements in combustion residues of coal, lignite, and biomass feedstocks

The combustion residues derived from coal, lignite, biomass, and spent wash could be recycled to extract critical elements required for energy transition. To recycle these elements from the combustion residues, it is necessary to understand their chemical mode of occurrence in the ash. This study presents the content of critical elements and their chemical mode of occurrence in coal, lignite, biomass, and incinerator ash. Lignite ash, rich in Ca and Si, offers Sc (31 mg/kg) and Nd (212 mg/kg), while coal ash, dominated by Si and Al, contains Ga (44.8 mg/kg). Biomass and spent wash ash, characterized by K, Ca, and S, present substantial potential for potash and Sc. Lignite ash primarily contains rare earth elements (REEs) in metal oxide-bound fractions, whereas in coal ash, the REEs are associated with the hard mullite or quartz phase. Biomass and incinerator ashes have significant water-soluble potash, and the Sc is associated with metal oxides. Green acids can extract critical elements from lignite, biomass, and incinerator ashes, but extracting from coal ash requires harsh conditions. Future research should concentrate on green extraction processes considering the chemical patterns of occurrence of critical elements.

Development of a hydroponic device using potassium Ion-Selective electrode and neural network technology

The rapid development of modern agricultural biotechnology and information technology has become a key driver of modern agricultural growth. The demand for ion detection is prevalent in all aspects of agriculture. This study details the research on an ion sensor agricultural system using potassium (K) ion-selective electrodes (ISEs). The main emphasis is on the application of artificial neural networks (ANNs) for driving ISE development of accuracy. ISEs based on solid contact with metal oxides, specifically manganese dioxide, are studied. Moreover, the design details of an ion signal acquisition device using the NI-9205 acquisition card and LabVIEW are presented. Finally, based on experimental results of nutrient solution samples, ANNs show better performance than the multiple linear regression method. The mean relative error of K-ISE detection was maintained within 4%. This study thoroughly discusses ISE technology to promote its adoption in agriculture.

Boosting nickel nanoferrite’s specific capacitance with Azadirachta Indica for advanced supercapacitors

Nickel Ferrite (NiFe2O4) a valuable transition metal oxide possessing a spinel structure, it is extensively utilized in industry due to its compelling properties. In this present study the sol–gel auto-combustion synthesis method was employed using nitrates and citric acid in conjunction with double distilled water (DDW) and Azadirachta Indica extract. The X-ray diffraction (XRD) analysis revealed the formation of a cubic spinel phase with high crystallinity. Crystallite size of prepared Nickel Ferrite in double distilled water and Azadirachta Indica by Scherrer’s equation and Williamson-Hall plot (W-H) are 28.09 nm and 33.01 nm as well as 16.23 nm and 16.55 nm, with microstrains of 0.32739 % and 0.339 × 10−3 % respectively. The notable reduction in the crystallite size is observed when employing Azadirachta Indica compared to the double distilled water-based synthesis. The X-ray density of the synthesized sample in double distilled water and Azadirachta Indica are obtained as 3.935 (g cm−3) and 5.427 (g cm−3). Transmission electron microscopy (TEM) of Azadirachta Indica-based nanostructured Nickel Ferrite material exhibited a particle size of 17.06 nm. The study encompassed the calculation of various parameters such as hopping lengths, polaron radius, specific surface area, packing fraction, and dislocation density. Magnetic parameters are comprehensively examined using a vibrating sample magnetometer (VSM), revealing a Bohr magneton is 3.278. The shifting of coercivity curve observed towards right due to exchange bias effect and the unidirectional anisotropy for diamagnetic Azadirachta Indica based Nickel ferrite. Optical properties are investigated through UV–VIS and Fourier-transform infrared (FTIR) spectroscopy, resulting in a band gap energy of 1.75 eV and a porosity is 11.16 %. Electrochemical evaluation of Nickel Ferrite electrodes is conducted over a potential range from 0.0 to 1 V. The specific capacitance of Nickel Ferrite electrodes synthesized with double distilled water and Azadirachta Indica are determined as 511.9 F/g and 695 F/g respectively, at a scan rate of 50 mV/s, as evaluated through cyclic voltammetry (CV) measurements in Ag/AgCl (0.1 M NaOH as electrolyte). The specific capacitance of Nickel Ferrite, produced with double distilled water and Azadirachta Indica extract, is 686 F/g and 817.398 F/g respectively, as determined by Galvanostatic charge–discharge (GCD) measurements. The study conclusively demonstrated significantly improvement in the electrochemical performance of Nickel Ferrite, synthesized with Azadirachta Indica extract for supercapacitor application. Based on GCD and CV, the specific capacitance has been boosted significantly with Azadirachta Indica extract for supercapacitor application.

Decoration of CeO2 nanoparticles on Cu/Co bimetallic oxide and their catalytic performance

We have developed a series of Co-Cu bimetallic oxide nanocatalysts using an environmentally friendly water phase synthesis method, demonstrating significant potential in catalyzing the CO oxidation reaction. The 0.3Co3O4/0.7CuO nano-hybrid, with a feed ratio of 3:7 for Cobalt(II) chloride hexahydrate to Copper(II) chloride dihydrate, exhibited a CO catalytic oxidation T90 approximately 70 °C lower than that of a single transition metal oxide material. Building on this, we enhanced the catalysts by incorporating CeO2 nanoparticles to produce Co3O4/CuO/CeO2 oxide nanocatalysts. By varying the amount of CeO2 nanoparticles added to the 0.3Co3O4/0.7CuO catalyst, we achieved further improvement in the CO oxidation performance. Specifically, the T90 of the CO catalytic oxidation reaction for the 0.3Co3O4/0.7CuO/0.7CeO2 material was approximately 30 °C lower than that of 0.3Co3O40.7CuO. Various characterization methods, such as XRD, EDX, and in situ FT-IR, were employed to investigate the impact of different components on the CO oxidation process and the potential reaction mechanism. The results indicated that the introduction of CeO2 successfully enhanced the activity and stability of the catalysts.

Metal heteroatoms significantly enhance efficacy of TiO2 nanomaterials in promoting hydrolysis of organophosphates: Implications for mitigating pollution of plastic additives.

Organophosphate esters (OPEs) are prevalent pollutants in the aquatic environment. OPEs are released from many sources, particularly, from the breakdown and weathering of plastic wastes, as OPEs are commonly used plastic additives. Metal oxide mineral nanoparticles play critical roles in the hydrolytic transformation of OPEs. While natural minerals often contain metal impurities, it is unclear how metal heteroatoms affect the efficiency of mineral nanoparticles in mediating hydrolysis reactions. Herein, we show that transition metal-doped anatase titanium dioxide (TiO2) nanomaterials are more effective in catalyzing the hydrolysis of 4-nitrophenyl phosphate (pNPP), a model OPE compound, with the relative effects of the heteroatoms following the order of Fe > Cr > Mn ≈ Ni > Co > Cu. With multiple lines of evidence based on spectroscopic analysis, kinetics modeling, and theoretical calculations, we show that metal doping increases the Lewis acidity of the TiO2 nanomaterials by increasing the oxidation state of surface Ti atoms, inducing oxygen vacancies, and creating additional Lewis acid sites with stronger acidities. Moreover, the increased amounts of surface hydroxyl groups due to metal-doping enhance inner-sphere complexation of pNPP through ligand exchange. The interesting observation that Fe-doped TiO2 exhibited the highest catalytic efficiency may have important implications for reducing the risks of organophosphate plastic additives, as iron is the most common heteroatom of naturally occurring TiO2 (nano)materials.

Waste biomass-based graphene oxide decorated with ternary metal oxide (MnO-NiO-ZnO) composite for adsorption of methylene blue dye

In this study, a novel approach for the removal of methylene blue (MB) dye is effectively illustrated by using biomass based composite adsorbent. The investigation employed areca nut husk (AH) to produce graphene oxide (GO) by a single step calcination method. Thereafter, AH-GO was incorporated by using ternary metal oxide (TMO) via hydrothermal treatment. The developed AH-GO@MnO-NiO-ZnO composite was characterized by various analytical techniques, including FT-IR, XRD, FESEM, HRTEM, BET surface area and Raman spectroscopy which exhibited promising properties for dye adsorption. To study the adsorption efficiency of prepared composite, optimization experiments were performed for adsorbent dose, initial dye concentration and contact time. The optimized parameters during adsorption phenomenon were found to be 0.5g/L of dose, 20mg/L of initial concentration and 180min of time exhibiting removal efficacy of 93.05 ± 0.93%. Moreover, adsorption isotherm and kinetic models were analysed to explore the adsorption behaviour of AH-GO@MnO-NiO-ZnO towards MB dye. The adsorption isotherm and kinetic studies followed Langmuir isotherm model and pseudo-second-order (PSO) model respectively. AH-GO@MnO-NiO-ZnO has demonstrated a maximum adsorption capability of 127.06mg/g. These findings collectively underscore the potential of AH-based adsorbent as a viable, inexpensive, and environment friendly for the treatment of wastewater contaminated with MB dye.

An analytical I-V model of SiC double-gate junctionless MOSFETs

Silicon carbide(SiC) double gate junctionless metal oxide semiconductor field-effect transistors(DG JL MOSFETs) have attracted significant attention due to their ideal high temperature characteristics and radiation resistance. Therefore, it is meaningful to exploit an I-V model for SiC DG JL MOSFETs. In this article, we make a linear approximation to describe the relationship between the surface mobile charge density and the surface electron concentration of the device. Based on this approximation and using the one-dimensional Poisson’s equation, we solve for the potential distribution of a SiC DG JL MOSFET in the subthreshold region. From this solution, we derived a functional relationship between the surface mobile charge density in the channel and the channel quasi-Fermi potential. Then we successfully developed a unified I-V model for the SiC DG JL MOSFETs. Based on the drain to source current calculation formula, the calculation expressions for the device’s transconductance and output conductance are derived. By comparing our model with the results from the two-dimensional numerical simulation software Silvaco Atlas, our model’s calculations closely match the two-dimensional numerical simulation results from the subthreshold region to the accumulation region. This model has reference significance for SiC DG JL MOSFETs in the high temperature electronic circuit application field.

CNT Functionalized GdCoBi Ternary Metal Oxide Nanocomposite for Electrochemical Detection of Perfluorooctanoic Acid and Energy Storage Applications

Perfluorooctanoic acid “Forever Chemical” presents substantial ecological challenges owing to its persistence and resistance to degradation. The study introduces a novel approach by integrating ternary metal oxides—Gd2O3, Co3O4, and Bi2O3 with carbon nanotubes to develop a versatile electrode material, CNT@GdCoBi NCs, which demonstrates dual functionality as both an electrochemical sensor for PFOA and a component for energy storage devices. The electrode exhibits outstanding electrochemical sensing performance, with a detection limit for PFOA of 4.9 ppb. Interference tests reveal the electrode's high selectivity for PFOA, with a tolerance limit of ≤5%. Practical application on various fruits, vegetables, and water samples shows an average relative standard deviation (%RSD) between 4.8 and 5.6%, underscoring the practical effectiveness of the CNT@GdCoBi NCs electrode. Furthermore, the CNT@GdCoBi NCs exhibit remarkable supercapacitor performance, achieving a specific capacitance of 1197F/g at 2A/g, which is 1.5 times higher than that of GdCoBi NCs. At a current density of 2A/g, the symmetric supercapacitor device demonstrates a specific capacitance of 269F/g, along with a high energy density of 52Wh/kg at a power density of 500W/kg. Additionally, the CNT@GdCoBi NCs electrode maintains good durability, retaining 94% of its capacitance after 10,000 cycles.

Design of alkali metal oxide adsorbent for direct air capture: Identification of physicochemical adsorption and analysis of regeneration mechanism

Direct air capture (DAC) represents an advanced negative carbon emission technology, with the key being high-performance CO2 adsorbents. First, this work carefully identifies CO2 physisorption and chemisorption by CaO/HcATP (CaO loaded on acid-modified attapulgite) as DAC adsorbent. The chemisorption of amorphous "CaO" plays a crucial role in both the adsorption capacity and rate, with contributions of 66.8 % and 50.85 %, respectively. The adsorption capacity of CaO/HcATP is only 212.4 ± 25.7 µmol/g via the simple CO2 physisorption and improved by 426.7 µmol/g owning to the chemisorption of amorphous CaO. Second, the concentration of silanol groups on CaO/HcATP plays a pivotal role in the adsorption process. The concentration of silanol groups decreases to 3.85 OH/nm2 after undergoing 30 cycles of adsorption-desorption. Then it increases to 9.54 OH/nm2 by adsorbing the moisture in the air, resulting in a recovered adsorption capacity of 90.7 %. Furthermore, the pseudo-first-order adsorption kinetics model effectively predicted the experimental results. Finally, the dual loop of CO2 capture and regeneration is summarized using the CaO/HcATP as DAC adsorbent. The amorphous "CaO" interacts with the surface silanol of HcATP, synergistically capturing CO2 in the form of "CaO···CO2", which reduces desorption energy consumption. The wetting property of HcATP contributes to the regeneration of CaO/HcATP. This work contributes to establishing fundamental principles for designing cost-effective DAC adsorbents.

Ternary metal oxide carbon composite as high-performance electrode material for supercapacitor applications

Recently, ternary metal oxides carbon composites recognized as metal organic frameworks (MOFs) have gained striking attention for supercapacitor electrode material due to high surface area, porosity, chemical stability, tunable properties, redox activity, and eco-friendly material. ZIF-67 is a novel MOF possessing these characteristics. Therefore, the present work reports the development of ternary iron-nickel–cobalt ZIF-67 composites (FeNiCo ZIF-67) using co-precipitation method with the variation in molar concentration of iron oxide, nickel oxide, and cobalt oxide. Physico-chemical characterizations of developed materials were investigated through X-ray diffraction (XRD), Raman spectroscopy, energy dispersive X-ray (EDX), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) to confirm the successful formation of composites and structure, morphology. Then, the electrodes were fabricated for all three synthesized composites and electrochemical analyses such as cyclic voltammetry (CV), galvanic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) were performed. The results revealed the porous polyhedral structure of FeNiCo ZIF-67 with different compositions consisting of interconnected nanoparticles played an important role in increasing the charge storage capacity of the material. Among the composites, FeNiCo ZIF-67 (1:2:1) electrode material achieved the highest specific capacitance of 532.7 F/g at a current density of 1 A/g. FeNiCo ZIF-67 (1:2:1) exhibited maximum electrochemical active surface area 89.12. Electrochemical impedance spectroscopy (EIS) demonstrated the minimal resistance of 7.8 Ω by FeNiCo ZIF-67 (1:2:1) composite electrode compared to the other two electrode materials. Cyclic stability study revealed the capacitance retention of 91 % after 10,000 continuous charge discharge cycles at a current density of 10 A/g. Electrode material demonstrated an outstanding electrochemical performance, and this work could provide a simple strategy to fabricate FeNiCo ZIF-67 nanostructured electrode materials for supercapacitors.

How to describe the time-dependent dissolution of engineered nanomaterials?

Numerous processes such as solubility, agglomeration/aggregation, or protein corona formation may change over time and significantly affect engineered nanomaterial (ENM) structure, property, and availability, resulting in their reduced or increased toxicological activity. Therefore, understanding the dynamics of these processes is essential for assessing and managing the risks of ENMs during their lifecycle, ensuring safety by design. Of these processes, the importance of solubility (i.e., the ability to release ions from the surface) is undeniable. Thus, we propose a practical approach, the Kalapus equation (KEq), to determine ENMs' dissolution over time. As a proof-of-concept, the KEq was applied to determine the solubility of six commercially used metal and metal oxide nanoparticles over time. The KEq exhibited a higher coefficient of determination (R2=0.995-0.999) than the logarithmic equation (R2=0.835-0.986), and the pseudo-first-order equation (R2=0.915-0.994) over a range of experimental data. The newly introduced Kalapus equation outperformed the logarithmic and pseudo-first-order equations when extrapolating beyond the time range in which solubility was experimentally determined. The mean absolute error in solubility prediction for the KEq was 3.29% and 4.28% for the first and second data points, respectively, significantly lower than the 13.46% and 18.05% observed for the pseudo-first-order/first-order equation. The proposed equation can be used as a part of New Generation Risk Assessment (NGRA) methodology, especially new Integrated Approaches to Testing and Assessments (IATAs).

Mo–V–Al–K–O catalyst for low-temperature oxidative dehydrogenation of propane

Compared with propane dehydrogenation (PDH) technology, oxidative dehydrogenation (ODH) of propane is an effective way to break through the thermodynamic constraints, which has changed the endothermic reaction into exothermic. Meanwhile, coking in PDH was significantly reduced by the presence of an oxidant in ODH of propane. Therefore, ODH of propane has attracted wide interest and has been studied in recent years. However, the contradiction between the conversion of propane and the selectivity of propene was the intrinsic problem of ODH of propane that required further study. In this work, a novel aluminum/potassium-doped mixed metal oxide catalyst Mo1V0.5Al0.02K0.03Ox was synthesized using a simple co-impregnation method, whose selectivity for propene (83.2 %) and conversion of propane (12.7 %) at 300 °C were the best among all other alkali metal/alkaline-earth metal-doped catalysts. The further discussion illustrated that doping potassium and alumina could synergistically adjust the density of acid sites on the catalyst, establishing an equilibrium between high propane conversion and the ideal propene selectivity. After modification, the density of Brønsted acid decreased, leading to an enhancement in the selectivity of propene. Simultaneously, the addition of steam in the feed gas promotes propene to oxygenates and improves the conversion of propane under the condition of constant contact time.

Pyrolysis of industrial hemp biomass from contaminated soil phytoremediation: kinetics, modelling transport phenomena and biochar-based metal reduction

Phytoremediation is the use of vegetation for the in situ treatment of contaminated environments. After plants have been used for phytoremediation of soils, their biomass can be used for example as value-added products or converted by thermochemical processes. Large-scale application of pyrolysis technology for phytoremediation biomass requires accurate predictive kinetic models and a characterization of the toxicity of the materials produced. The pyrolysis of industrial hemp (Cannabis sativa L.) was investigated on a laboratory scale by varying the process conditions and accurately modelled by considering four pseudo-components with first reaction order. The average value of the coefficients of determination is 0.9980. Biomass and biochar were characterized and the main components of the gas phase were monitored. We found Cd, Pb, and Zn in the roots, although in lower amounts than in the soil. Especially the leaves and stems showed negligible traces of these elements, so that these parts can be used directly, even if the hemp was grown on the polluted soil. After pyrolysis, the concentration of pollutants in the solid fraction decreased, which could be attributed to the reduction of metal oxides (or salts) to elemental form and subsequent evaporation. This pyrolysis process has the potential to treat heavy metal-rich biomass, with gas phase purification via condensation, yielding agricultural-grade biochar, CO-rich gas and a highly concentrated heavy metal stream in absorbent material.

Specific and high-affinity adsorption of volatile organic compounds on titanium dioxide surface.

The interaction between metal oxides and volatile organic compounds (VOCs) from the ambient atmosphere plays an important role in environmental and catalytic applications. Previous scanning probe microscopy and x-ray spectroscopy studies revealed surprisingly that the TiO2 [rutile (110)] surface selectively adsorbed atmospheric carboxylic acids, which typically exist in only parts-per-billion concentrations. In this work, we used in situ sum-frequency vibrational spectroscopy to study the interaction between rutile (110) and typical VOC molecules, including formic acid, acetic acid, and formaldehyde. Spectra from all three adsorbed molecules on rutile (110) were similar to the rutile surface spectrum in the ambient atmosphere, showing a broad resonance near 2950cm-1 that can be attributed to the bridging bidentate adsorption of corresponding compounds. In contrast, on a fused silica surface, a molecular monodentate adsorption configuration was observed for all the molecules, with aliphatic carbons appearing to be the dominant adventitious species.

Redox Self-Equilibration in Molecular Vanadium Oxide Mixtures Enables Multi-Electron Storage.

Polyoxometalates (POMs) are ideal components for reversible multi-electron storage in energy technologies. To-date, most redox-applications employ only single, individual POM species, which limits the number of electrons that can be stored within a given potential window. Here, we report that spontaneous redox self-equilibration during cluster synthesis leads to the formation of two structurally related polyoxovanadates which subsequently aggregate into co-crystals. This results in systems with significantly increased redox reactivity. The mixed POM system was formed by non-aqueous self-assembly of a vanadate precursor in the presence of Mg2+, resulting in two mixed-valent (VIV/V) species, [(MgOH)V13O33Cl]4- (={MgV13}) and the di-vanadium-functionalized species [V14O34Cl]4- (={V14}), which co-crystallize in a 1 : 1 molar stoichiometry. Experimental data indicate that in the native state, {MgV13} is reduced by three electrons, and {V14} is reduced by five electrons. Electrochemical studies in solution show, that the system can reversibly undergo up to fourteen redox transitions (tentatively assigned to twelve 1-electron processes and two 2-electron processes) in the potential range between -2.15 V to +1.35 V (vs Fc+/Fc). The study demonstrates how highly redox-active, well-defined molecular mixtures of mixed-valent molecular metal oxides can be accessed by redox-equilibration during synthesis, opening new avenues for molecular energy storage.

Redox‐Selbstequilibrierung in molekularen Vanadiumoxid‐ Mischungen ermöglicht Multi‐ Elektronenspeicherung

AbstractPolyoxometallate (POM) sind ideale Komponenten für die reversible Multielektronenspeicherung in der Energietechnik. Bislang werden in den meisten Redox‐Anwendungen nur einzelne POM‐Spezies verwendet, was die Anzahl der Elektronen, die innerhalb eines bestimmten Potenzialfensters gespeichert werden können, begrenzt. Hier berichten wir, dass eine spontane Redox‐ Selbstequilibrierung während der Clustersynthese zur Bildung von zwei strukturell verwandten Polyoxovanadaten führt, die anschließend zu Ko‐Kristallen aggregieren. Dies führt zu Systemen mit deutlich erhöhter Redox‐Reaktivität. Das gemischte POM‐System wurde durch nichtwässrige Selbstassemblierung einer Vanadat‐Vorstufe in Gegenwart von Mg2+ gebildet, was zu zwei gemischtvalenten (VIV/V) Spezies führte, [(MgOH)V13O33Cl]4− (={MgV13}) und der Di‐Vanadium‐funktionalisierten Spezies [V14O34Cl]4− (={V14}), die in einer 1 : 1‐Molstöchiometrie ko‐kristallisieren. Experimentelle Daten zeigen, dass {MgV13} im nativen Zustand um drei Elektronen und {V14} um fünf Elektronen reduziert ist. Elektrochemische Untersuchungen in Lösung zeigen, dass das System reversibel bis zu vierzehn Redoxübergänge (vorläufig zwölf 1‐Elektronen‐Prozesse und zwei 2‐Elektronen‐Prozessen zugeordnet) im Potenzialbereich zwischen −2,15 V und +1,35 V (gegen Fc+/Fc) durchlaufen kann. Die Studie zeigt, wie hochgradig redoxaktive, wohldefinierte Mischungen aus gemischtvalenten molekularen Metalloxiden durch Redox‐ Selbstequilibrierung während der Synthese zugänglich gemacht werden können, was neue Möglichkeiten für die molekulare Energiespeicherung eröffnet.

Pd Nanoparticles Decorated CeZrOx for Enhanced Photocatalytic Hydrogenation of Biomass‐Derived Compounds

AbstractThe photocatalytic conversion of biomass‐derived compounds into value‐added chemicals presents a promising protocol for the sustainable production of renewable chemicals. Our study explores the hydrogenation of biomass model compounds under visible light illumination. Zr was incorporated into the CeO2 framework, forming a CeZrOx(1:0.5) solid solution, confirmed by powder X‐ray diffraction (PXRD) and X‐ray photoelectron spectroscopy (XPS) analyses. The light uptake capacity of the CeZrOx solid solution was characterized using UV–visible spectroscopy. Additionally, the band structure of the CeZrOx solid solution was assessed using valance band X‐ray photoelectron spectroscopy (VB‐XPS) and Ultraviolet photoelectron spectroscopy (UPS) analysis, revealing a Z‐Scheme, which was further confirmed by various control experiments. Upon decorating the CeZrOx(1:0.5) solid solution with 1 wt% palladium (Pd), the resulting 1Pd/CeZrOx(1:0.5) composite exhibited improved charge separation and enhanced visible light absorption capacity. This composite achieved ∼99% conversion of furfural to tetrahydrofurfuryl alcohol under a 15 W blue LED illumination and 0.2 MPa hydrogen. Similarly, it demonstrated ∼99% conversion of benzyl phenyl ether (BPE) to toluene and phenol under a 10 W blue LED illumination. Our findings elucidate the active sites and demonstrate the recyclability of mixed metal oxides for selective furfural hydrogenation and BPE hydrogenolysis under visible light.

Designing Artificial Laccase Catalysts by Introducing Substrate Oxidation Metals into Oxygen-Reducing Metal-Organic Frameworks: Cu-Doped ZIF-67.

Laccase, a multi-copper oxidase, is limited by its optimal temperature range and isolation costs. To overcome these challenges, we synthesized copper-doped zeolitic imidazolate framework-67 (Cu-doped ZIF-67) with 16 mol % Cu as an artificial laccase catalyst. The introduced Cu site acts as the phenol oxidation site, and Co-based ZIF-67 is the four-electron oxygen reduction site. Laccase also employs this division of oxidation and reduction sites. Cu-doped ZIF-67 demonstrated significant catalytic activity, superior to natural laccase, especially at elevated temperatures, and maintained stability across multiple reaction cycles. These findings suggest that Cu-doped ZIF-67 is a robust, reusable alternative for industrial applications requiring high thermal stability and efficient catalysis.

High-temperature carbon dioxide capture in a porous material with terminal zinc hydride sites.

Carbon capture can mitigate point-source carbon dioxide (CO2) emissions, but hurdles remain that impede the widespread adoption of amine-based technologies. Capturing CO2 at temperatures closer to those of many industrial exhaust streams (>200°C) is of interest, although metal oxide absorbents that operate at these temperatures typically exhibit sluggish CO2 absorption kinetics and instability to cycling. Here, we report a porous metal-organic framework featuring terminal zinc hydride sites that reversibly bind CO2 at temperatures above 200°C-conditions that are unprecedented for intrinsically porous materials. Gas adsorption, structural, spectroscopic, and computational analyses elucidate the rapid, reversible nature of this transformation. Extended cycling and breakthrough analyses reveal that the material is capable of deep carbon capture at low CO2 concentrations and high temperatures relevant to postcombustion capture.