Generation Of Oxygen Vacancies Research Articles

Rapid Hydrolysis Precipitation of BiOBr Nanosheets for Boosting Photocatalytic N2 Fixation

AbstractIn this paper, BiOBr nanosheets were synthesized through a novel hydrolysis precipitation method, which significantly reduced energy consumption and time cost compared to traditional hydrothermal synthesis methods. The subjected hydrothermal and high‐temperature calcination process promote the generation of surface oxygen vacancies, which inhibited the recombination of photogenerated electron hole pairs and improve the photocatalytic performance of BiOBr. Additionally, by adjusting the addition amount of KOH in the synthesis process, BiOBr can grow towards more complex crystal structure, which also provides a new path for the fabrication of 2D materials.

The origin of exceptionally large ductility in molybdenum alloys dispersed with irregular-shaped La2O3 nano-particles

Molybdenum and its alloys are known for their superior strength among body-centered cubic materials. However, their widespread application is hindered by a significant decrease in ductility at lower temperatures. In this study, we demonstrate the achievement of exceptional ductility in a Mo alloy containing rare-earth La2O3 nanoparticles through rotary-swaging, a rarity in Mo-based materials. Our analysis reveals that the large ductility originates from substantial variations in the electronic density of states, a characteristic intrinsic to rare-earth elements. This characteristic can accelerate the generation of oxygen vacancies, facilitating the amorphization of the oxide-matrix interface. This process promotes vacancy absorption and modification of dislocation configurations. Furthermore, by inducing irregular shapes in the La2O3 nanoparticles through rotary-swaging, incoming dislocations interact with them, creating multiple dislocation sources near the interface. These dislocation sources act as potent initiators at even reduced temperatures, fostering diverse dislocation types and intricate networks, ultimately enhancing dislocation plasticity.

Effect of Boron Content in LiOH Solutions on the Corrosion Behavior of Zr-Sn-Nb Alloy

In pressurized water reactors, LiOH may be concentrated in some areas, leading to the accelerated corrosion of fuel claddings. Injecting boric acid into primary coolants can mitigate the accelerated corrosion effect of LiOH on Zircaloys, but the effects of boron content on the corrosion behavior of the Zr-Sn-Nb alloy are still unknown. This work focused on the corrosion and hydrogen absorption behavior at 360 °C/18.6 MPa in 100 mg/kg LiOH solutions with 0 mg/kg, 50 mg/kg, and 200 mg/kg boron contents for up to 510 days, aiming to study the effect of boron content on corrosion resistance in LiOH solutions. Corrosion kinetics, microstructures of oxide films, hydrogen absorption concentrations and hydride morphology were obtained after the test. The results show that injecting boron in LiOH solutions can significantly reduce the corrosion weight gain, hydrogen concentration, and hydrogen length of Zr-Sn-Nb alloys, that is, improving corrosion resistance effectively. During the oxidation of the Zr-Sn-Nb alloy, B3+ and Li+ incorporate in oxide films. The incorporation of Li+ may lead to the generation of oxygen vacancies, which can carry oxygen from the solutions to O/M interface, accelerating corrosion. The incorporation of B3+ in oxide films will slow down the oxidation of Zr-Sn-Nb alloys by reducing the oxygen vacancies caused by Li+ aggregation.

Efficient Charge Injection for Perovskite Light‐Emitting Transistor

AbstractMetal halide perovskite semiconductors have demonstrated remarkable performance in light‐emitting‐diode applications in recent years. However, their potential application in other emerging optoelectronic devices, such as light‐emitting field‐effect transistors (LEFETs) is impeded by poor luminous efficiency due to inefficient charge injection. Here, an n‐type MgZnInO (MIZO) as the channel layer is synthesized to achieve efficient electron injection in perovskite LEFETs. These findings indicate that the incorporation of Mg not only suppresses the generation of oxygen vacancies but also optimizes the energy level alignment. These synergistic effects reduce non‐radiative recombination and improve interfacial charge transport. Consequently, the MIZO‐based perovskite LEFETs exhibit an improvement in threshold voltage, subthreshold swing, and field‐effect mobility. The electroluminescence performance shows a peak external quantum efficiency (EQE) of 1.97% with a maximum brightness of 2.1 × 104 cd m−2, accompanied by low‐efficiency roll‐off (an EQE of 1.88% at the current density of 810 mA cm−2). To the best of the author's knowledge, this represents the best luminous efficiency reported for perovskite LEFETs to date.

Zn promoted GaZrOx ternary solid solution oxide combined with SAPO-34 effectively converts CO2 to light olefins with low CO selectivity.

We proposed a new strategy for CO2 hydrogenation to prepare light olefins by introducing Zn into GaZrOx to construct ZnGaZrOx ternary oxides, which was combined with SAPO-34 to prepare a high-performance ZnGaZrOx/SAPO-34 tandem catalyst for CO2 hydrogenation to light olefins. By optimizing the Zn doping content, the ratio and mode of the two-phase composite, and the process conditions, the 3.5%ZnGaZrOx/SAPO-34 tandem catalyst showed excellent catalytic performance and good high-temperature inhibition of the reverse water-gas shift (RWGS) reaction. The catalyst achieved 26.6% CO2 conversion, 82.1% C2=-C4= selectivity and 11.8% light olefins yield. The ZnGaZrOx formed by introducing an appropriate amount of Zn into GaZrOx significantly enhanced the spillover H2 effect and also induced the generation of abundant oxygen vacancies to effectively promote the activation of CO2. Importantly, the RWGS reaction was also significantly suppressed at high temperatures, with the CO selectivity being only 46.1% at 390°C.

Vacancy-rich Fe-Ce mixed oxides as nanoenzymes for efficient antioxidant activity in vitro

Traditional anti-oxidant drugs possess limited active sites and short half-lives that hamper the efficiency of the removal of excessive reactive oxygen species (ROS) that are linked to various diseases. On this point, the CeO2 nanozyme has recently attracted much attention because of its anti-oxidant ability to act as a ROS scavenger. While introducing trivalent ions into CeO2 helps induce the increasing Ce3+, it may damage the auto-regenerative ability and finally lead to decreased ROS activities. Here, Fe-Ce mixed oxides (Fe-CeO2) is developed as a nanozyme with adjustable oxygen vacancies. The ROS scavenging capabilities of Fe-CeO2 outperformed those of CeO2, primarily due to a higher concentration of oxygen vacancies. Moreover, the auto-regenerative properties of CeO2 are still retained after forming Fe-Ce mixed oxides. To delve into the enhanced scavenging activity driven by the increasing oxygen vacancies, we employ density functional theory (DFT) calculations to provide a comprehensive explanation, which can be attributed to the stimulated generation of oxygen vacancies and the more energetically favorable reaction path. This study provides a more profound understanding of the structure–activity relationship in nanozymes and inspires a novel approach for a highly efficient ROS scavenger via defect engineering.

Poly(3,4-ethylenedioxythiophene) encapsulation/intercalation boosting stability and zinc ion storage properties of vanadyl phosphates

The electrochemical properties of vanadyl phosphates as cathode materials for Zn-ion batteries have been severely hindered by their inherent poor electronic conductivity, unavoidable dissolution in aqueous solutions, and sluggish reaction kinetics. In this study, poly(3,4-ethylenedioxythiophene) (PEDOT) is introduced in vanadyl phosphates (PEDOT-VOP) through the in situ polymerization as interlayer guest species and surface coating layer, along with the generation of oxygen vacancies. The intercalated PEDOT develops strong interaction with the host layer, which can maintain its structural integrity. In addition, the PEDOT coating shell can enhance electronic conductivity together with oxygen vacancies to promote efficient electron transfer and prevent dissolution of active materials to stabilize the vanadyl phosphate core. As a result, the PEDOT-VOP electrode demonstrates a high discharge capacity of 180 mA h g−1 at 0.1 A/g with good rate performance (128 mA h g−1 at 2 A/g) and enhanced cycling stability (a capacity retention of 88.6 % after 2000 cycles at 1 A/g). The reversible Zn2+ insertion/extraction mechanism is further validated by diverse ex situ tests.

Light-assisted thermochemical reduction of CuFe2O4 within a photo-thermogravimetric analyser for solar fuel production

The solar thermochemical cycle has emerged as a promising clean energy technology that enables the splitting of water for solar fuel production. However, conventional two-step thermochemical cycles using single-metal oxides require high operating temperatures above 1000 °C, especially for the reduction step. Typical solar thermal systems struggle to meet such high temperature requirements, making it vital to reduce the operating temperature. To find a solution enabling lower temperature requirements, we propose a photo-thermochemical reduction (PTR) strategy, which employs light illumination as assistance, combining both thermally induced and photo-induced effects for more generation of oxygen vacancies (VOs), within the oxygen carrier copper ferrite (CuFe2O4). Experimental studies were performed in a specially-designed photo-thermogravimetric analyser (photo-TGA) that directly measures the weight change of solid reactants under direct light illumination. The results indicate that the PTR achieves a decrease of nearly 40 °C in temperature requirements, giving a higher oxygen release of 21% compared to that driven by pure thermal heating at 800 °C. We also measured an increase of 0.09 in the non-stoichiometry parameter δ in the photo-TGA. Additionally, we observed that oxygen release increases distinctly with the light intensity of incident illumination. From the viewpoint of spectral ranges, ultraviolet and visible light illumination give the primary boost to the generation of photo-induced VOs. These results demonstrate the effective assistance of concentrated solar energy to enhance the two-step thermochemical cycle for solar fuel production at lower temperatures.

Microwave-Solvothermal Synthesis of Mesoporous CeO2/CNCs Nanocomposite for Enhanced Room Temperature NO2 Detection

Nitrogen dioxide (NO2) gas sensors are pivotal in upholding environmental integrity and human health, necessitating heightened sensitivity and exceptional selectivity. Despite the prevalent use of metal oxide semiconductors (MOSs) for NO2 detection, extant solutions exhibit shortcomings in meeting practical application criteria, specifically in response, selectivity, and operational temperatures. Here, we successfully employed a facile microwave-solvothermal method to synthesize a mesoporous CeO2/CNCs nanocomposite. This methodology entails the rapid and comprehensive dispersion of CeO2 nanoparticles onto helical carbon nanocoils (CNCs), resulting in augmented electronic conductivity and an abundance of active sites within the composite. Consequently, the gas-sensing sensitivity of the nanocomposite at room temperature experienced a notable enhancement. Moreover, the presence of cerium oxide and the conversion of Ce3+ and Ce4+ ions facilitated the generation of oxygen vacancies in the composites, thereby further amplifying the sensing performance. Experimental outcomes demonstrate that the nanocomposite exhibited an approximate 9-fold increase in response to 50 ppm NO2 in comparison to pure CNCs at room temperature. Additionally, the CeO2/CNCs sensor displayed remarkable selectivity towards NO2 when exposed to gases such as NH3, CO, SO2, CO2, and C2H5OH. This straightforward microwave-solvothermal method presents an appealing strategy for the research and development of intelligent sensors based on CNCs nanomaterials.

Highly selective and stable electrochemical reduction of nitrate to ammonia using VO2-x/CuF catalyst with oxygen vacancies

Electrocatalytic reduction poses significant challenges due to slow kinetics, limited selectivity, and instability, hindering its potential for sustainable nitrate (NO3−) removal and producing valuable N-containing compounds. This study develops a one-step hydrothermal approach for decorating copper foam (CuF) with VO2 nanobelts. Subsequently, N2 annealing is performed to generate oxygen vacancies (OVs) and yield a VO2-x/CuF sample for its application as an electrocatalyst in reducing NO3− to ammonia (NH3). Several characterization techniques are applied to study the structural and morphological features of the VO2-x/CuF sample, which shows a high crystalline and defective bundle-like structure of nanobelts attributed to the release of oxygen atoms that are beneficial for the electrochemical NO3− reduction processes. The VO2-x/CuF sample demonstrates impressive results, with a NO3− conversion of 78.7 %, an NH4+ yield rate of 1.833 mmol h−1 cm−2, an NH4+ FE of 77.9 %, and a remarkable NH4+ selectivity of 99.7 % at −1.3 V vs RHE. It is worth mentioning that the isotopic labeling findings reveal that the NH4+ originated from NO3− during the electrocatalytic NO3− reduction using a VO2-x/CuF sample. This confinement method effectively creates accessible metallic catalysts with OVs, enabling high-activity, selective and stable NO3− reduction to NH4+ electrocatalysts.

Stable CO2 Reduction under Natural Air on Ni-Sn Hydroxide Photocatalyst with Dynamic Renewable Oxygen Vacancies.

Advanced photocatalysts are highly desired to activate the photocatalytic CO2 reduction reaction (CO2RR) with low concentration. Herein, the NiSn(OH)6 with rich surface lattice hydroxyls was synthesized to boost the activity directly under the natural air. Results showed that terminal Ni-OH could serve as donors to feed protons and generate oxygen vacancies (VO), thus beneficial to convert the activated CO2 (HCO3-) mainly into CO (5.60 μmol/g) in the atmosphere. It was flexible and widely applicable for a stable CO2RR from high pure to air level free of additionally adding H2O reactant, and higher than the traditional gas-liquid-solid (1.58 μmol/g) and gas-solid (4.07 μmol/g) reaction system both using high pure CO2 and plenty of H2O. The strong hydrophilia by the rich surface hydroxyls allowed robust H2O molecule adsorption and dissociation at VO sites to achieve the Ni-OH regeneration, leading to a stable CO yield (11.61 μmol/g) with the enriched renewable VO regardless of the poor CO2 and H2O in air. This work opens up new possibilities for the practical application of natural photosynthesis.

Layered double oxide (CoAl-LDO) catalysis for enhanced ozonation of methyl orange: Performance assessment and mechanistic insights

In this study, we report the successful synthesis of a novel layered double oxide (CoAl-LDO) ozone catalyst through co-precipitation and high-temperature calcination method, utilizing layered double hydroxide (CoAl-LDH) as an uncalcined intermediate product. The synthesized CoAl-LDO exhibits a thinner and more curved plate-like morphology with well-developed porous structures, demonstrating richer content of active oxygen species and enhanced oxygen migration ability. Notably, the CoAl-LDO catalyst demonstrates superior catalytic performance compared to conventional catalysts and ozone alone systems. Utilizing methyl orange (MO) as the target pollutant, CoAl-LDO catalyzed ozonation achieved an impressive removal rate of 88.27 % within 10 min, surpassing the performance of CoAl-LDH (61.84 %), Co3O4 (57.71 %), and O3 alone systems (47.71 %). Moreover, the CoAl-LDO catalyst exhibited excellent stability and reusability, maintaining a removal rate above 72.13 % over four consecutive cycles. In addition, we propose a novel reaction mechanism for the catalytic ozonation based on the interconversion of Co2+ and Co3+ during the reaction process to generate oxygen vacancies (OV), which in turn react with water molecules and ozone molecules to produce ROS (especially O2−). These findings provide unique perspectives for the precise design and rational application of ozone catalysts.

Catalytic oxidation of dichloromethane over W-Nb composite oxide catalysts modified by Co: The influence of redox ability and acidity

Catalytic oxidation of highly toxic chlorinated volatile organic compounds often places high demands on the anti-poisoning ability of the catalysts. Here, Co/WNb catalysts with different Co loadings were prepared for the catalytic oxidation of dichloromethane (DCM). Notably, the interaction between the active components and the carriers resulted in a high Co2+/Co3+ ratio on the catalyst surface, which facilitated the generation of oxygen vacancies (Ov) and enhanced the redox properties of the catalyst. Furthermore, the WNb carrier offered ample surface acidic sites, bolstering the catalyst's resilience against chlorine poisoning. The study revealed that achieving a more balanced combination of redox properties and acidity was beneficial for enhancing the catalytic degradation efficiency of DCM. 3% Co/WNb exhibited the best catalytic activity (T90 = 269 °C). The catalyst also exhibited excellent stability and outstanding water resistance. Potential reaction routes for the catalytic oxidation of DCM were explored using in-situ IR spectra analysis. This study offers novel insights for the development of efficient, stable, and environmentally friendly catalysts for DCM degradation.

Optimising Ion Conductivity in NdBaInO4-Based Phases

Based on the previous work conducted by Fujii et al., NdBaInO4 compounds present modest oxide-ion conductivities. Therefore, it has been an attractive system of significant interest. In this study, we attempted to partially substitute Ca for Nd and the total electrical conductivity was successfully improved due to the generation of oxygen vacancies. The synthesis, crystal structure, density, surface topography, and electrical properties of NdBaInO4 and Ca-doped NdBaInO4 have been studied, respectively. NdBaInO4 and 10% and 20% molar fractions of Ca-doped NdBaInO4 were synthesized through solid-state reactions. The crystal structure of them was obtained from Le Bail refinement of the XRD pattern, giving the result of the monoclinic structure, which belongs to P21/c space group. The highest total electrical conductivity of 4.91 × 10−3 S cm−1 was obtained in the Nd0.9Ca0.1BaInO3.95 sample at a temperature of 760 °C in the dry atmosphere and the activation energy was reduced from 0.68 eV to 0.58 eV when the temperature was above 464 °C (737 K) after doping the NdBaInO4 with a 0.1 molar fraction of Ca2+. Moreover, the total conductivity of Nd0.9Ca0.1BaInO3.95 in the wet atmosphere at moderate temperature was relatively higher than that in the dry atmosphere, which suggests that potential proton conduction may exist in wet atmospheres. In addition, the oxygen diffusion coefficients of Nd0.9Ca0.1BaInO3.95 (D* = 1.82 × 10−8 cm2/s, 850 °C) was about two times higher than that of Nd0.8Ca0.2BaInO3.90 (D* = 7.95 × 10−9 cm2/s, 850 °C) and was increased significantly by two orders of magnitude when compared with the oxygen diffusion coefficient of the undoped NdBaInO4 (D* = 8.25 × 10−11 cm2/s, 850 °C).

Ferroelectric SrMnO3 Thin Film Grown on (110)‐Oriented PMN‐PT Substrate

Exploring the unique physical properties of oxide perovskites necessitates their growth on diverse single‐crystal substrates. The thin‐film growth of perovskite SrMnO3 (SMO) has been a particular focus of research due to its emerging room‐temperature multiferroicity. Herein, the epitaxial thin films of (110)‐oriented SMO are grown on the piezoelectric (110)‐oriented (1–x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 (PMN‐PT) substrate. The effects of the thickness and oxygen annealing on the crystal structure, stoichiometry, and ferroelectric properties of the SMO thin film are systematically investigated. The tensile strain produced by the lattice mismatch between the bulk SMO and the PMN‐PT substrate causes an expansion of the c‐lattice parallel to the in‐plane direction of the substrate. The films show larger a‐, b‐, and c‐lattice parameters than the bulk material, resulting in volume expansion of the unit cell. This lattice expansion is attributed to the generation of oxygen vacancies driven by the reduced formation energy caused by the high elastic strain. Piezoelectric force microscopy reveals that the SMO film contains domains with strain‐mediated in‐plane and vacancy‐mediated out‐of‐plane polarization. Furthermore, the piezoelectric response of the PMN‐PT substrate effectively modulates the biaxial tensile strain in the SMO film, offering a potential strategy for controlling the crystal structure and ferroelectric properties of SMO.

Amplifying chlorinated phenol decomposition via Dual-Pathway O2 Activation: The impact of zirconium loading on BiOCl

The effectiveness of photocatalytic molecular oxygen (O2) activation in pollutant removal relies on the targeted production of reactive oxygen species (ROS). Herein, we demonstrate the dual-pathway activation of O2 on BiOCl through zirconium (Zr) loading. The incorporation of Zr onto the surface of BiOCl not only leads to an increased generation of oxygen vacancies (OV) but also fosters a coupling between the d electrons of Zr and OV, forming dual-active sites known as Zr-oxygen vacancies (Zr-OV). Generally, OV adsorbs O2 and transfers one electron directly to form superoxide radicals (•O2–). Contrary to the conventional single-electron direct activation of O2 to form •O2–, Zr-OV exhibits more flexible coordination and superior electron-donating capabilities. It facilitates O2 conversion to peroxide radicals (O22–) and enables the subsequent generation of •O2– from O22–, significantly promotes the dechlorination and mineralization efficiency of chlorophenol under visible light. This study presents a straightforward strategy to precisely regulate ROS production by expanding pathways, shedding light on the critical role of managing ROS generation for effective pollutant purification.

Facet-dependent in-situ formation of oxygen vacancy and plasmonic Bi in BiOBr nanosheets and resultant influence on the generation and separation of charge carriers

The development of advanced photoactive materials has aroused widespread interest, but is severely plagued by the inherent narrow photo-responsive range and rapid recombination of electrons and holes. In this study, the unconventional BiOBr nanosheets decorated with Bi0 and oxygen vacancies (OVs) are successfully synthesized through a facial one-pot hydrothermal method, followed by heat treatment. Cetyltrimethylammonium bromide and mannitol contribute to the selective exposure of (001) and (010) facets, respectively. The absence of the outermost Br atoms facilitates the simultaneous generation of OVs and Bi0 on the surface during heating, forming the Schottky junction. The synergy of SPR in the Bi0 metal, OVs and Schottky junction can effectively enhance the light absorption and charge separation. This work proposes and verifies a feasible approach to construct defects in-situ by regulating the crystal facets and manipulating the surface atomic arrangement and coordination.

Guided Design of Efficient Oxygen Evolution Catalysts Using Patent Analysis.

The facile and rapid design of efficient oxygen evolution reaction (OER) catalysts holds paramount significance for energy conversion devices, such as water electrolyzers and fuel cells. Despite substantial progress in catalyst synthesis and performance exploration, the design and selection processes remain inefficient. In this context, we integrate patent analysis with catalyst design, leveraging the scholarly research functionalities within patent analyses to aid in the design and synthesis of a NiFeRu-carbon catalyst as a high-performance OER catalyst. The results demonstrate that the NiFeRu-Carbon catalyst with low Ru loading (0.3 wt %) exhibits an overpotential of only 219 mV at 10 mA cm-2 under alkaline conditions, and after continuous operation for 200 h, the overpotential only attenuates by 15 mV. The incorporation of high-valence Ru dopants elevated the intrinsic activity of individual catalytic sites within NiFe-layered double hydroxides (LDHs). During the catalytic process, the partial dissolution of Ru might lead to the generation of numerous oxygen vacancies within NiFe- LDH, thereby enhancing the catalyst's activity and stability.

Interfacial oxygen vacancy engineering and built-in electric field mediated Z-scheme In2O3/Ag3PO4 heterojunction for boosted photocatalytic doxycycline degradation

Doxycycline pollutants in environment seriously destroy the balance of ecological system. A Z-scheme In2O3/Ag3PO4 heterojunction is constructed by attaching Ag3PO4 nanoparticles on hollow In2O3 hexagonal prism structures for efficient degradation of doxycycline. The doxycycline (30 mg/L) removal rate by IAO-1 (mole ratio of In2O3:Ag3PO4 is 1:3, 1.0 g/L) reaches 99.7% under visible light irradiation. Degradation rates are almost unchanged after five cycles of degradation experiments, demonstrating the excellent reusability and stability of the IAO-1 photocatalyst. The photocatalytic degradation of doxycycline in different water matrices by IAO-1 shows excellent performance, which provides significant potential for practical applications. The experiments and DFT results demonstrate that the built-in electric fields in IAO-1 contribute to the charge transfer from Ag3PO4 to In2O3, leading to the formation of a Z-scheme heterojunction with high redox capacity. The hollow defect structure of IAO-1 effectively activates molecular oxygen to generate oxygen vacancies and induce 1O2 production through energy transfer, which promotes the attack of benzene rings and oxygen-containing groups in the molecular structure of doxycycline, leading to hydroxylation, demethylation, and ring-opening reactions. This work provides new ideas for constructing Z-scheme photocatalysts with oxygen vacancies and built-in electric fields for practical wastewater treatment.

Low-nuclearity CuZn ensembles on ZnZrOx catalyze methanol synthesis from CO2

Metal promotion could unlock high performance in zinc-zirconium catalysts, ZnZrOx, for CO2 hydrogenation to methanol. Still, with most efforts devoted to costly palladium, the optimal metal choice and necessary atomic-level architecture remain unclear. Herein, we investigate the promotion of ZnZrOx catalysts with small amounts (0.5 mol%) of diverse hydrogenation metals (Re, Co, Au, Ni, Rh, Ag, Ir, Ru, Pt, Pd, and Cu) prepared via a standardized flame spray pyrolysis approach. Cu emerges as the most effective promoter, doubling methanol productivity. Operando X-ray absorption, infrared, and electron paramagnetic resonance spectroscopic analyses and density functional theory simulations reveal that Cu0 species form Zn-rich low-nuclearity CuZn clusters on the ZrO2 surface during reaction, which correlates with the generation of oxygen vacancies in their vicinity. Mechanistic studies demonstrate that this catalytic ensemble promotes the rapid hydrogenation of intermediate formate into methanol while effectively suppressing CO production, showcasing the potential of low-nuclearity metal ensembles in CO2-based methanol synthesis.