The Contact Interface Electronic Coupling of Cobalt and Zirconia Enables Stable and Highly Efficient 4e- Oxygen Reduction Reaction Catalysis.

Cobalt (Co) is an efficient oxygen reduction reaction (ORR) catalyst but suffers from issues of easy deactivation and instability. Here, it shows that ZrO2 can stabilize Co through interface electron coupling and enables highly efficient 4e- ORR catalysis. Porous carbon nanofibers loaded with dispersed Co-nanodots (≈10 nm, 9.63 wt%) and ZrO2 nanoparticles are synthesized as the catalyst. The electron transfer from the metallic Co to ZrO2 causes interface-oriented electron enrichment that promotes the activation and conversion of O2, improving the efficiency of 4e- transfer. Moreover, the simulation results show that ZrO2 acts like an electron reservoir to store electrons from Co and slowly release them to the interface, solving the easy deactivation problem of Co. The catalyst exhibits a high half-wave potential (E1/2) of 0.84 V, which only decreases by 3.6 mV after 10 000 cycles, showing great stability. Particularly, the enhanced spin polarization of Co in a magnetic field reinforces the interface electron coupling that increases the E1/2 to 0.864 V and decreases the energy barrier of ORR from 0.81 to 0.63 eV, confirming that the proposed strategy is effective for constructing efficient and stable ORR catalysts.

Non-enzymatic electrochemical impedance sensor for selective detection of electro-inactive organophosphate pesticides using Zr-MOF/ZrO2/MWCNT ternary composite.

The existence of multiple pesticide residues in fruits and vegetables constitutes a direct peril to living organisms. Therefore, it is crucial to develop a low-cost screening method for determining organophosphate pesticides (OPPs) in food samples. This study describes the solvothermal synthesis of a ternary composite comprising multi-walled carbon nanotubes (MWCNT), zirconium oxide, and a zirconium-metal-organic framework (Zr-MOF). The ternary composite was characterised using XRD, FESEM, FTIR, and BET. The ternary composite provides a large surface area (1158 m2/g) compared with the pristine Zr-MOF (868 m2/g). The composite-modified glassy carbon electrode was used to determine nine pesticides, including organophosphate (malathion, dimethoate, chlorpyrifos, monocrotophos, and glyphosate) and non-organophosphate (thiophanate methyl, carbendazim, atrazine, and 2,4, D). In particular, various chemical combinations of OPPs were selected, such as S-P=S, P=S, P=O, and non-OPPs such as C=S (with sulphur), and without sulphur. The sensor results show that the sensor selectivity is high for OPPs containing both phosphorus and sulphur molecules. The low detection limit of the sensor was 2.02, 2.8, 2.5, 1.11, and 2.01 nM for malathion, chlorpyrifos, dimethoate, monocrotophos, and glyphosate, respectively. The electrode exhibited significant chemical stability (93%) after 100 cycles, good repeatability, and a long shelf life. The sensor is reliable for qualitative real-time applications.

Te4+ and Er3+ doped ZrO2 nanoparticles with enhanced photocatalytic, antibacterial activity and dielectric properties: A next generation of multifunctional material.

Amid rising water contamination from industrial sources, tackling toxic dyes and pathogens is critical. Photocatalysis offers a cost-effective and eco-friendly solution to this pressing challenges. Herein, we synthesized Te4+ and Er3+ doped ZrO2 photocatalysts through hydrothermal method and investigated their efficacy in degrading Congo red (CR) and pathogens under visible light. XRD and Raman Spectroscopy confirm monoclinic and tetragonal mixed-phases without any impurities. Doping-induced defects, reduced crystalline diameter, high surface area, modified bandgap (2.95 eV), photoluminescence quenching, coupled with interfacial polarization, contribute to EZO's excellent dielectric response (1.149 × 106), for achieving remarkable photocatalytic activity, verified by photoelectrochemical measurements, LC-MS and phytotoxicity analysis. Under optimal conditions, EZO achieves 99% CR degradation within 100 min (TOC 79.9%), surpassing ZO (77%) and TZO (84%). Catalyst dosages, dye concentrations, and solution pH effect on EZO's photocatalytic performance are systematically assessed. Scavenging experiment emphasized the pivotal role of · OH in CR degradation with 96.4% efficiency after 4 cycles, affirming its remarkable stability. Moreover, EZO demonstrates ROS-mediated antibacterial activity against E. faecalis and E. coli bacteria under visible light, achieving >97% and >94% inhibition rate with an inhibition zone > 3 mm. Hence, the nanoparticle's dual action offers a practical solution for treating contaminated wastewater, ensuring safe irrigation.

MOF-Derived ZrO2-Supported Bimetallic Pd-Ni Catalyst for Selective Hydrogenation of 1,3-Butadiene.

A series of MOF-derived ZrO2-supported Pd-Ni bimetallic catalysts (PdNi/UiO-67-CTAB(n)-A500) were prepared by co-impregnation and pyrolysis at 500 °C under air atmosphere using UiO-67-CTAB(n) (CTAB: cetyltrimethylammonium bromide; n: the concentration of CTAB; n = 0, 3, 8, 13, 18) as a sacrificial template. The catalytic activity of PdNi/UiO-66-CTAB(n)-A500 in 1,3-butadiene hydrogenation was found to be dependent on the crystal morphology of the UiO-67 template. The highest activity was observed over the PdNi/UiO-67-CTAB(3)-A500 catalyst which was synthesized using UiO-67-CTAB(3) with uniform octahedral morphology as the template for the 1,3-butadiene selective hydrogenation. The 1,3-butadiene conversion and total butene selectivity were 98.4% and 44.8% at 40 °C within 1 h for the PdNi/UiO-67-CTAB(3)-A500 catalyst, respectively. The catalyst of PdNi/UiO-67-CTAB(3)-A500 can be regenerated in flowing N2 at 200 °C. Carbon deposited on the surface of the catalyst was the main reason for its deactivation. This work is valuable for the high-efficiency bimetallic catalyst's development on the selective hydrogenation of 1,3-butadiene.

Structure and Chemical Reactivity of Y-Stabilized ZrO2 Surfaces: Importance for the Water-Gas Shift Reaction.

The surface structure and chemical properties of Y-stabilized zirconia (YSZ) have been subjects of intense debate over the past three decades. However, a thorough understanding of chemical processes occurring at YSZ powders faces significant challenges due to the absence of reliable reference data acquired for well-controlled model systems. Here, we present results from polarization-resolved infrared reflection absorption spectroscopy (IRRAS) obtained for differently oriented, Y-doped ZrO2 single-crystal surfaces after exposure to CO and D2O. The IRRAS data reveal that the polar YSZ(100) surface undergoes reconstruction, characterized by an unusual, red-shifted CO band at 2132 cm-1. Density functional theory calculations allowed to relate this unexpected observation to under-coordinated Zr4+ cations in the vicinity of doping-induced O vacancies. This reconstruction leads to a strongly increased chemical reactivity and water spontaneously dissociates on YSZ(100). The latter, which is an important requirement for catalysing the water-gas-shift (WGS) reaction, is absent for YSZ(111), where only associative adsorption was observed. Together with a novel analysis Scheme these reference data allowed for an operando characterisation of YSZ powders using DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy). These findings facilitate rational design and tuning of YSZ-based powder materials for catalytic applications, in particular CO oxidation and the WGS reaction.

Selective Upcycling of Polyethylene Terephthalate towards High-valued Oxygenated Chemical Methyl p-Methyl Benzoate using a Cu/ZrO2 Catalyst.

Upgrading of polyethylene terephthalate (PET) waste into valuable oxygenated molecules is a fascinating process, yet it remains challenging. Herein, we developed a two-step strategy involving methanolysis of PET to dimethyl terephthalate (DMT), followed by hydrogenation of DMT to produce the high-valued chemical methyl p-methyl benzoate (MMB) using a fixed-bed reactor and a Cu/ZrO2 catalyst. Interestingly, we discovered the phase structure of ZrO2 significantly regulates the selectivity of products. Cu supported on monoclinic ZrO2 (5 %Cu/m-ZrO2 ) exhibits an exceptional selectivity of 86 % for conversion of DMT to MMB, while Cu supported on tetragonal ZrO2 (5 %Cu/t-ZrO2 ) predominantly produces p-xylene (PX) with selectivity of 75 %. The superior selectivity of MMB over Cu/m-ZrO2 can be attributed to the weaker acid sites present on m-ZrO2 compared to t-ZrO2 . This weak acidity of m-ZrO2 leads to a moderate adsorption capability of MMB, and facilitating its desorption. Furthermore, DFT calculations reveal Cu/m-ZrO2 catalyst shows a higher effective energy barrier for cleavage of second C-O bond compared to Cu/t-ZrO2 catalyst; this distinction ensures the high selectivity of MMB. This catalyst not only presents an approach for upgrading of PET waste into fine chemicals but also offers a strategy for controlling the primary product in a multistep hydrogenation reaction.

Hybrid MOF Template-Directed Construction of Hollow-Structured In2 O3 @ZrO2 Heterostructure for Enhancing Hydrogenation of CO2 to Methanol.

Direct hydrogenation of CO2  to methanol using green hydrogen has emerged as a promising method for carbon neutrality, but qualifying catalysts represent a grand challenge. In2 O3 /ZrO2  catalyst has been extensively applied in methanol synthesis due to its superior activity; however, the electronic effect by strong oxides-support interactions between In2 O3  and ZrO2  at the In2 O3 /ZrO2  interface is poorly understood. In this work, abundant In2 O3 /ZrO2  heterointerfaces are engineered in a hollow-structured In2 O3 @ZrO2  heterostructure through a facile pyrolysis of a hybrid metal-organic framework precursor MIL-68@UiO-66. Owing to well-defined In2 O3 /ZrO2  heterointerfaces, the resultant In2 O3 @ZrO2  exhibits superior activity and stability toward CO2  hydrogenation to methanol, which can afford a high methanol selectivity of 84.6% at a conversion of 10.4% at 290 °C, and 3.0 MPa with a methanol space-time yield of up to 0.29 gMeOH  gcat -1  h-1 . Extensive characterization demonstrates that there is a strong correlation between the strong electronic In2 O3 -ZrO2  interaction and catalytic selectivity. At In2 O3 /ZrO2  heterointerfaces, the electron tends to transfer from ZrO2  to In2 O3  surface, which facilitates H2  dissociation and the hydrogenation of formate (HCOO*) and methoxy (CH3 O*) species to methanol. This study provides an insight into the In2 O3 -based catalysts and offers appealing opportunities for developing heterostructured CO2  hydrogenation catalysts with excellent activity.

Stabilizing High Density Cu Active Sites with ZrO2 Quantum Dots as Chemical Ligand in N-doped Porous Carbon Nanofibers for Efficient ORR.

The emerging transition metal-nitrogen-carbon (MNC) materials are considered as a promising oxygen reduction reaction (ORR) catalyst system to substitute expensive Pt/C catalysts due to their high surface area and potential high catalytic activity. However, MNC catalysts are easy to be attacked by the ORR byproducts that easily lead to the deactivation of metal active sites. Moreover, a high metal loading affects the mass transfer and stability, but a low loading delivers inferior catalytic activity. Here, a new strategy of designing ZrO2 quantum dots and N-complex as dual chemical ligands in N-doped bubble-like porous carbon nanofibers (N-BPCNFs) to stabilize copper (Cu) by forming CuZrO3-x /ZrO2 heterostructures and CuN ligands with a high loading of 40.5 wt.% is reported. While the highly porous architecture design of N-BPCNFs builds a large solidelectrolytegas phase interface and promotes mass transfer. The preliminary results show that the half-wave potential of the catalyst reaches 0.856 V, and only decreases 0.026 V after 10 000 cycles, exhibiting excellent stability. The proposed strategy of stabilizing metal active sites with both heterostructures and CuN ligands is feasible and scalable for developing high metal loading ORR catalyst.

Voltage- and Power-Conversion Performance of Bi-functional ZrO2 : Er3+ / Yb3+ Assisted and Co-sensitized Dye Sensitized Solar Cells for Internet of Things Applications.

Giant power conversion efficiency is achieved by using bifunction ZrO2 : Er3+ /Yb3+ assisted co-sensitised dye-sensitized solar cells. The evolution of the crystalline structure and its microstructure are examined by X-ray diffraction, scanning electron microscopy studies. The bi-functional behaviour of ZrO2 : Er3+ /Yb3+ as upconversion, light scattering is confirmed by emission and diffused reflectance studies. The bi-function ZrO2 : Er3+ /Yb3+ (pH=3) assisted photoanode is co-sensitized by use of N719 dye, squaraine SPSQ2 dye and is sandwiched with Platinum based counter electrode. The fabricated DSSC exhibited a giant power conversion efficiency of 12.35 % with VOC of 0.71 V, JSC of 27.06 mA/cm2 , FF of 0.63. The results, which motivated the development of a small DSSC module, gave 6.21 % and is used to drive a tiny electronic motor in indoor and outdoor lighting conditions. Small-area DSSCs connected in series have found that a VOC of 4.52 V is sufficient to power up Internet of Things (IoT) devices.

Ultra-thin ZrO2overcoating on CuO-ZnO-Al2O3catalyst by atomic layer deposition for improved catalytic performance of CO2hydrogenation to dimethyl ether.

An ultra-thin overcoating of zirconium oxide (ZrO2) film on CuO-ZnO-Al2O3(CZA) catalysts by atomic layer deposition (ALD) was proved to enhance the catalytic performance of CZA/HZSM-5 (H form of Zeolite Socony Mobil-5) bifunctional catalysts for hydrogenation of CO2to dimethyl ether (DME). Under optimal reaction conditions (i.e. 240 °C and 2.8 MPa), the yield of product DME increased from 17.22% for the bare CZA/HZSM-5 catalysts, to 18.40% for the CZA catalyst after 5 cycles of ZrO2ALD with HZSM-5 catalyst. All the catalysts modified by ZrO2ALD displayed significantly improved catalytic stability of hydrogenation of CO2to DME reaction, compared to that of CZA/HZSM-5 bifunctional catalysts. The loss of DME yield in 100 h of reaction was greatly mitigated from 6.20% (loss of absolute value) to 3.01% for the CZA catalyst with 20 cycles of ZrO2ALD overcoating. Characterizations including hydrogen temperature programmed reduction, x-ray powder diffraction, and x-ray photoelectron spectroscopy revealed that there was strong interaction between Cu active centers and ZrO2.

Tuning the Interaction between Platinum Single Atoms and Ceria by Zirconia Doping for Efficient Catalytic Ammonia Oxidation.

Aiming at the development of an efficient NH3 oxidation catalyst to eliminate the harmful NH3 slip from the stationary flue gas denitrification system and diesel exhaust aftertreatment system, a facile ZrO2 doping strategy was proposed to construct Pt1/CexZr1-xO2 catalysts with a tunable Pt-CeO2 interaction strength and Pt-O-Ce coordination environment. According to the results of systematic characterizations, Pt species supported on CexZr1-xO2 were mainly in the form of single atoms when x ≥ 0.7, and the strength of the Pt-CeO2 interaction and the coordination number of Pt-O-Ce bond (CNPt-O-Ce) on Pt1/CexZr1-xO2 showed a volcanic change as a function of the ZrO2 doping amount. It was proposed that the balance between the reasonable concentration of oxygen defects and limited surface Zr-Ox species well accounted for the strongest Pt-CeO2 interaction and the highest CNPt-O-Ce on Pt/Ce0.9Zr0.1O2. It was observed that the Pt/Ce0.9Zr0.1O2 catalyst exhibited much higher NH3 oxidation activity than other Pt/CexZr1-xO2 catalysts. The mechanism study revealed that the Pt1 species with the stronger Pt-CeO2 interaction and higher CNPt-O-Ce within Pt/Ce0.9Zr0.1O2 could better activate NH3 adsorbed on Lewis acid sites to react with O2 thus resulting in superior NH3 oxidation activity. This work provides a new approach for designing highly efficient Pt/CeO2 based catalysts for low-temperature NH3 oxidation.

Electronic structure and defect-induced luminescence study of phase-stabilized t-ZrO2 nanocrystals.

Luminescent tetragonal-ZrO2 (t-ZrO2 ) nanocrystals were synthesized using an optimized combustion method without post-synthesis annealing and characterized using X-ray diffraction, electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, UV-Vis. spectroscopy, photoluminescence spectroscopy, thermoluminescence (TL), and vibrating sample magnetometry. The as-synthesized t-ZrO2 nanocrystals have a bandgap of 4.65 eV and exhibit defect-assisted blue emission (Commission Internationale de I'Elcairage coordinates 0.2294, 0.1984) when excited at 270 nm. The defect states were qualitatively and quantitatively analyzed using TL after irradiating nanocrystals with γ- and UV radiations at various doses. The TL glow curves show intense emission in the high-temperature region from 523 to 673 K for both UV- and γ-irradiated samples; however, another less-intense TL peak was also observed in the low-temperature region from 333 to 453 K with γ irradiation at higher doses, indicating the formation of shallow trapping states. The activation energies, frequency factor, and order of kinetics were estimated using the computerized glow curve deconvolution method for the shallow and deep traps for γ- and UV-irradiated samples. The present study shows that phase-stabilized t-ZrO2 nanocrystals are potential candidates for luminescence-based applications.

Luminescence properties of Ce-doped ZrO2 phosphors synthesized by combustion method.

Zr1-x Cex O2 with x = 0.005, 0.01, 0.02, and 0.03 samples were synthesized using a combustion technique. The X-ray diffraction results revealed that Ce-doped ZrO2 nanoparticles were in a monoclinic structure up to 1 mol% Ce concentration. The increase in the Ce concentration caused more distortion in the monoclinic structure of zirconia. The samples showed a mixed phase (monoclinic + tetragonal) beyond 1 mol% Ce content. The crystallite size (D) and strain (ε) were calculated from the Williamson-Hall equation. The D decreased from 25 ± 1 to 20 ± 1 nm and ε increased from 0.03 to 0.28% with an increase in Ce concentration. Photoluminescence (PL) spectra of Zr1-x Cex O2 showed emission in the blue region under an excitation wavelength of 290 nm. Zr0.995 Ce0.005 O2 showed the highest PL intensity with an average lifetime of 0.93 µs, and the PL intensity decreased with the increase in the Ce concentration. Thermoluminescence (TL) glow curves of Zr1-x Cex O2 were measured after gamma irradiation (500 Gy) with a heating rate of 5 K s-1 . The TL curve of Zr0.995 Ce0.005 O2 showed two prominent peaks at 412 K (peak 1) and 600 K (peak 2). The first TL glow peak was shifted towards a higher temperature at 440 K above 1 mol% Ce concentration. Repetitive TL measurements on the same aliquot exhibited excellent repeatability. Kinetic parameters associated with the TL peaks were calculated using the curve fitting method. Peak 1 followed non-first-order kinetics. The value of the activation energy of the 440 K peak was found to be 0.95 ± 0.01 eV for Zr0.99 Ce0.01 O2 . These findings showed that Zr1-x Cex O2 might be used in lighting and radiation dosimeter applications.

The planar anodic Al2O3-ZrO2 nanocomposite capacitor dielectrics for advanced passive device integration.

The need for integrated passive devices (IPDs) emerges from the increasing consumer demand for electronic product miniaturization. Metal-insulator-metal (MIM) capacitors are vital components of IPD systems. Developing new materials and technologies is essential for advancing capacitor characteristics and co-integrating with other electronic passives. Here we present an innovative electrochemical technology joined with the sputter-deposition of Al and Zr layers to synthesize novel planar nanocomposite metal-oxide dielectrics consisting of ZrO2 nanorods self-embedded into the nanoporous Al2O3 matrix such that its pores are entirely filled with zirconium oxide. The technology is utilized in MIM capacitors characterized by modern surface and interface analysis techniques and electrical measurements. In the 95-480 nm thickness range, the best-achieved MIM device characteristics are the one-layer capacitance density of 112 nF·cm-2, the loss tangent of 4·10-3 at frequencies up to 1 MHz, the leakage current density of 40 pA·cm-2, the breakdown field strength of up to 10 MV·cm-1, the energy density of 100 J·cm-3, the quadratic voltage coefficient of capacitance of 4 ppm·V-2, and the temperature coefficient of capacitance of 480 ppm·K-1 at 293-423 K at 1 MHz. The outstanding performance, stability, and tunable capacitors' characteristics allow for their application in low-pass filters, coupling/decoupling/bypass circuits, RC oscillators, energy-storage devices, ultrafast charge/discharge units, or high-precision analog-to-digital converters. The capacitor technology based on the non-porous planar anodic-oxide dielectrics complements the electrochemical conception of IPDs that combined, until now, the anodized aluminum interconnection, microresistors, and microinductors, all co-related in one system for use in portable electronic devices.

Visualization of the Final Stage of Sintering in Nanoceramics with Atomic Resolution.

The deep understanding of the sintering mechanism is pivotal to optimizing denser ceramics production. Although several models explain the sintering satisfactorily on the micrometric scale, the extrapolation for nanostructured systems is not trivial. Aiming to provide additional information about the particularities of the sintering at the nanoscale, we performed in situ experiments using high-resolution transmission electron microscopy (HRTEM). We studied the pore elimination process in a ZrO2 thin film and identified a high anisotropic pore elimination. Interestingly, there is a redistribution of the atoms from the rough surface in the solid-gas surface, followed by the atom attachment in a faceted surface. Finally, we found evidence of the pore acting as a pin, reducing the GB mobility. These findings certainly can contribute to enhance the kinetic models to describe the densification process of systems at the nanoscale.

Molecular Dynamics Approach to the Physical Mixture of In2O3 and ZrO2: Defect Formation and Ionic Diffusion.

Recent research on the use of physical mixtures In2O3-ZrO2 has raised interesting questions as to how their combination enhances catalytic activity and selectivity. Specifically, the relationship between oxygen diffusion and defect formation and the epitaxial tension in the mixture should be further investigated. In this study, we aim to clarify some of these relationships through a molecular dynamics approach. Various potentials for the two oxides are compared and selected to describe the physical mixture of In2O3 and ZrO2. Different configurations of each single crystal and their physical mixture are simulated, and oxygen defect formation and diffusion are measured and compared. Significant oxygen defect formation is found in both crystals. In2O3 seems to be stabilized by the mixture, while ZrO2 is destabilized. Similar results were found for the ZrO2 doping with In and ln2O3 doping with Zr. The results explain the high activity and selectivity catalyst activity of the mixture for the production of isobutylene from ethanol.

New Carbamoyl Surface-Modified ZrO2 Nanohybrids for Selective Au Extraction from E-Waste.

Efficient and selective extractions of precious and critical metal ions such as Au(III) and Pd(II) were investigated using zirconia nanoparticles surface modified with different organic mono- and di-carbamoyl phosphonic acid ligands. The modification is made on the surface of commercial ZrO2 that is dispersed in aqueous suspension and was achieved by optimizing the Bronsted acid-base reaction in ethanol/H2O solution (1:2), resulting in inorganic-organic systems of ZrO2-Ln (Ln: organic carbamoyl phosphonic acid ligand). The presence, binding, amount, and stability of the organic ligand on the surface of zirconia nanoparticles were confirmed by different characterizations such as TGA, BET, ATR-FTIR, and 31P-NMR. Characterizations showed that all the prepared modified zirconia had a similar specific surface area (50 m2.g-1) and the same amount of ligand on the zirconia surface in a 1:50 molar ratio. ATR-FTIR and 31P-NMR data were used to elucidate the most favorable binding mode. Batch adsorption results showed that (i) ZrO2 surface modified with di-carbamoyl phosphonic acid ligands had the highest adsorption efficiency to extract metals than mono-carbamoyl ligands, and (ii) higher hydrophobicity of the ligand led to better adsorption efficiency. The surface-modified ZrO2 with di-N,N-butyl carbamoyl pentyl phosphonic acid ligand (ZrO2-L6) showed promising stability, efficiency, and reusability in industrial applications for selective gold recovery. In terms of thermodynamic and kinetic adsorption data, ZrO2-L6 fits the Langmuir adsorption model and pseudo-second-order kinetic model for the adsorption of Au(III) with maximum experimental adsorption capacity qmax = 6.4 mg.g-1.

Coating zirconium oxide-nanocomposite with humic acid for recovery of mercury and chromium in hazardous waste of chemical oxygen demand test.

Hazardous waste of chemical oxygen demand (COD) test (HWCOD) is one of the most common laboratory wastewaters, containing large amounts of H2SO4 and highly toxic Cr3+ and Hg2+. Current treatment methods suffered from incomplete removal of Cr3+ and high-cost. Herein, a humic acid-coated zirconium oxide-resin nanocomposite (HA-HZO-201) was fabricated for efficient recovery of Cr3+ and Hg2+ in HWCOD. The synthesized HA-HZO-201 shows excellent tolerance to wide pH range (1-5) and high salinity (3.5 mol/L NaCl), as well as adsorption capacity for Cr3+ (37.5 mg/g) and Hg2+ (121.3 mg/g). After treating with HA-HZO-201 by using a fixed-bed adsorption procedure, the final Cr3+ and Hg2+ concentrations in HWCOD decreased to 0.28 and 0.02 mg/L, respectively. In addition, the HA-HZO-201 can be regenerated by desorption and recovery of Cr3+ and Hg2+ using HNO3 and thiourea as eluents, respectively. After 5 cycles of adsorption/desorption, the removal efficiencies still reach up to 86.0% for Cr3+ and 89.7% for Hg2+, indicating an excellent regeneration of HA-HZO-201. We hope this work open new opportunities for treatment of HWCOD with high-efficiency and low-cost.

Dual active sites over Cu-ZnO-ZrO2 catalysts for carbon dioxide hydrogenation to methanol.

CO2 hydrogenation to methanol is a significant approach to tackle the problem of global warming and simultaneously meet the demand for the portable fuel. Cu-ZnO catalysts with various kinds of promoters have received wide attention. However, the role of promoter and the form of active sites in CO2 hydrogenation are still in debate. Here, various molar ratios of ZrO2 were added into the Cu-ZnO catalysts to tune the distributions of Cu0 and Cu+ species. A volcano-like trend between the ratio of Cu+/ (Cu+ + Cu0) and the amount of ZrO2 is presented, among which the CuZn10Zr (the molar ratio of ZrO2 is 10%) catalyst reaches the highest value. Correspondingly, the maximum value of space-time yield to methanol with 0.65 gMeOH/(gcat·hr) is obtained on CuZn10Zr at reaction conditions of 220°C and 3 MPa. Detailed characterizations demonstrate that dual active sites are proposed during CO2 hydrogenation over CuZn10Zr catalyst. The exposed Cu0 takes participate in the activation of H2, while on the Cu+ species, the intermediate of formate from the co-adsorption of CO2 and H2 prefers to be further hydrogenated to CH3OH than decomposing into the by-product of CO, yielding a high selectivity of methanol.

Reaction-Induced Metal-Metal Oxide Interactions in Pd-In2 O3 /ZrO2 Catalysts Drive Selective and Stable CO2 Hydrogenation to Methanol.

Ternary Pd-In2 O3 /ZrO2 catalysts exhibit technological potential for CO2 -based methanol synthesis, but developing scalable systems and comprehending complex dynamic behaviors of the active phase, promoter, and carrier are key for achieving high productivity. Here, we show that the structure of Pd-In2 O3 /ZrO2 systems prepared by wet impregnation evolves under CO2 hydrogenation conditions into a selective and stable architecture, independent of the order of addition of Pd and In phases on the zirconia carrier. Detailed operando characterization and simulations reveal a rapid restructuring driven by the metal-metal oxide interaction energetics. The proximity of InPdx alloy particles decorated by InOx layers in the resulting architecture prevents performance losses associated with Pd sintering. The findings highlight the crucial role of reaction-induced restructuring in complex CO2 hydrogenation catalysts and offer insights into the optimal integration of acid-base and redox functions for practical implementation.