Non-noble Metal Catalysts Research Articles

Trace Iron-Modified CeO₂-supported Core-shell CoO@Co Catalyst for Selective Conversion of Furfural to 1,5-Pentanediol.

In the conversion of furfural using non-noble metal catalysts, preferential cleavage of the C2-O bond followed by hydrogenation of the C=C bond facilitates selective access to valuable 1,5-pentanediol (1,5-Ped). Herein, we developed CeO₂ loaded core-shell CoO@Co nanoparticle catalysts. Adjusting Co loading, Fe doping, and reduction temperature improved reaction efficiency. 7Co-0.2Fe/CeO₂ catalysts reduced at 500 °C demonstrated optimal performance. 1,5-Ped produced at 54.76 mmol/g(Co)/h, representing the top activity levels among the reported catalysts. H₂-TPR, XRD, HAADF-STEM, FT-IR, XPS, and XANES were employed to investigate the catalyst structure-activity relationship. Co²⁺ cleaves furan ring C-O bond, Co⁰ promotes double-bond hydrogenation. The CoO@Co structure favors the desired 1,5-Ped production route. Trace Fe species optimize the Co²⁺/Co⁰ ratio, enhance the substrate adsorption, and inhibit the furan ring saturation. These findings emphasize the importance of fine-tuning catalyst structure and composition for selectivity improvement.

Single-atom Barium Promoter Enormously Enhanced Non-noble Metal Catalyst for Ammonia Decomposition.

As a well-established topic, single-atom catalyst has drawn growing interest for its high utilization of metal. However, researchers prefer to develop various active metals with single-atom form, the intrinsic roles of single-atom promoters are usually underrated, which are significant in boosting reaction activity. In this work, Ba single atoms were in situ prepared in the Co-Ba/Y2O3 catalyst with crystallized BaCO3 as the precursor under the ammonia decomposition reaction condition. The optimized Co-Ba/Y2O3 catalyst achieves extremely high H2 production rate of 138.3 mmolH2·gcat-1·min-1 at very low temperature (500 °C, GHSV = 840,000 mL·g-1·h-1) and Co-Ba/Y2O3 exhibits excellent durability during the 350 h test, which realizes the highest activity among all non-noble catalysts, and reaches or even exceeds numerous reported Ru-based catalysts. Both Y2O3 and Co demonstrate positive interactions with Ba, which significantly facilitates the dispersion of Ba species at high temperatures (≥ 600 °C). Ba single atoms significantly enhance the charge density of Co and form additionally active Co-O-Ba-Y2O3 interfacial sites, which alleviates hydrogen poisoning and decreases the reaction barrier of the N-H bond activation of *NH. The exploration of atomically dispersed promoters is groundbreaking in heterogeneous catalysis, which opens up a whole new domain of catalytic material.

Non-Noble Metal Catalysts for Electrooxidation of 5-Hydroxymethylfurfural.

2,5-Furandicarboxylic acid (FDCA) is a class of valuable biomass-based platform compounds. The creation of FDCA involves the catalytic oxidation of 5-hydroxymethylfurfural (HMF). As a novel catalytic method, electrocatalysis has been utilized in the 5-hydroxymethylfurfural oxidation reaction (HMFOR). Common noble metal catalysts show catalytic activity, which is limited by price and reaction conditions. Non-noble metal catalyst is known for its environmental friendliness, affordability and high efficiency. The development of energy efficient non-noble metal catalysts plays a crucial role in enhancing the HMFOR process. It can greatly upgrade the demand of industrial production, and has important research significance for electrocatalytic oxidation of HMF. In this paper, the reaction mechanism of HMF undergoes electrocatalytic oxidation to produce FDCA are elaborately summarized. There are two reaction pathways and two oxidation mechanisms of HMFOR discussed deeply. In addition, the speculation on the response of the electrode potential to HMFOR is presented in this paper. The main non-noble metal electrocatalysts currently used are classified and summarized by targeting metal element species. Finally, the paper focus on the mechanistic effects of non-noble metal catalysts in the reaction, and provide the present prospects and challenges in the electrocatalytic oxidation reaction of HMF.

Modified Si Oxidation Behavior by Ultrathin Ni Catalyst Enabling Oxidant-Less Metal-Assisted Chemical Etching.

Metal-assisted chemical etching (MACE), a wet-based anisotropic etching process for semiconductors, has emerged as an alternative to plasma-based etching. However, using noble metal catalysts in MACE limits the implementation of complementary metal-oxide-semiconductor (CMOS) processes. This study explores Si etching using an ultrathin Ni catalyst as a novel approach for MACE. The thickness of the Ni catalyst emerges as a critical parameter, with 1 nm of Ni proving to be the optimal thickness to achieve smooth and deep etching. Unlike conventional MACE methods, the ultrathin Ni catalyst enables Si etching without strong oxidants. Wafer-scale Si etching demonstrates the versatility of the ultrathin Ni catalyst in producing various microstructures. It is found that the ultrathin Ni/Si interfacial state plays a crucial role in influencing the Si reactivity, lowering the barrier for Si oxidation. CMOS-compatible and cost-efficient ultrathin Ni makes MACE a promising alternative for semiconductor nanofabrication. This study pioneers MACE using an ultrathin non-noble metal catalyst, offering valuable insights for researchers in this field.

Localized surface plasmon resonance effect-mediated in-situ photochemical–formation of H2O2 for high epoxidation performance over LaSrCoNiO6 nanoparticles

Selective aerobic epoxidation of allylic alcohols and olefins presents a promising solution to the modern chemical industry. However, the development of non-noble metal catalysts with superior catalytic performance for this reaction remains a significant challenge. This study introduces a plasmonic photothermal-catalytic system centered around nano LaSrCoNiO6 (LSCNi-N) catalyst, enabling the epoxidation of cinnamyl alcohol and styrene mediated by LSPR effect under visible light illumination (>420 nm). This catalyst exhibits superior epoxidation catalytic performance, with selectivities of up to 72.3 % in a 93.4 % conversion of cinnamyl alcohol and 91.8 % selectivity of styrene oxide at almost 100 % conversion of styrene. Mechanistic studies reveal that the high selectivity derives from the in-situ photochemical formation of H2O2 mediated by the localized surface plasmon resonance effect of LSCNi-N and hole scavenger effect of cinnamyl alcohol. These findings highlight the potential of designing plasmonic transition-metal oxidic catalysts to overcome challenges in selectively synthesizing fine chemicals through visible light catalysis.

Sustained hydrogen production through alkaline water electrolysis using Bridgman–Stockbarger derived indium-impregnated copper chromium selenospinel

The depletion of conventional fossil fuels necessitates the development of sustainable energy alternatives, with electrochemical water splitting for hydrogen (H2) production being a promising solution. However, large-scale hydrogen generation is hindered by the scarcity of cost-effective electrocatalysts to replace noble metals such as Pt and RuO2 in the Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER). In this study, we report the synthesis of CuCr2-xInxSe4 (x = 0, 0.2, 0.4) using a dual approach combining the Bridgman-Stockbarger method and ball milling. Among the synthesized materials, CuCr1.8In0.2Se4 demonstrates outstanding HER activity in 1.0 M KOH, achieving a potential of −0.16 V vs. RHE at a current density of 10 mA cm−2. Moreover, the material shows remarkable durability during a three-electrode accelerated degradation test in an alkaline medium, maintaining its performance over 24 h at a constant current density of −200 mA cm−2, with a stable potential of −0.57 V vs. RHE. Additionally, CuCr1.8In0.2Se4 was tested in a two-electrode configuration alongside CoFe LDH, achieving a benchmark of 1.7 V for overall water splitting. It sustained a current density of 400 mA cm−2 for 24 h in an accelerated degradation test, exhibiting a minimal loss of 0.1 V after the testing period. These results highlight CuCr1.8In0.2Se4 as a promising non-noble metal catalyst for HER, demonstrating its potential to reduce reliance on noble materials for large-scale hydrogen production.

Recent Progress in Non-Noble Metal Catalysts for Oxygen Evolution Reaction: A Focus on Transition and Rare-Earth Elements.

The demand for renewable energy sources has become more urgent due to climate change and environmental pollution. The oxygen evolution reaction (OER) plays a crucial role in green energy sources. This article primarily explores the potential of using non-noble metals, such as transition and rare earth metals, to enhance the efficiency of the OER process. Due to their cost-effectiveness and unique electronic structure, these non-noble metals could be a game-changer in the field. 'Doping,' which is the process of adding a small amount of impurity to a material to alter its properties, and 'synergistic effects,' which refer to the combined effect of two or more elements that is greater than the sum of their individual effects, are two key concepts in this field. Transition and rare earth metals can reduce the overpotential, a measure of the excess potential required to drive a reaction, thus enhancing the OER process by engineering the electronic and surface molecular structure. This article summarizes the roles of various non-noble metals in the OER process and highlights opportunities for researchers to propose innovative ways to optimize the OER process.

Na-doped cobalt spinel electrocatalysts prepared by programmed electrostatic spraying for improving OER activity and durability in acidic media

The daunting challenge to establish a trade-off among the activity, durability, and cost of electrocatalysts for oxygen evolution reaction (OER) with sluggish reaction kinetics impedes the practical green energy conversion. Hereby, a non-noble metal-based electrocatalyst (i.e., Na-doped Co3O4) was in-situ prepared by programmed electrostatic spraying as an advanced alternative to the costly and scarce state-of-the-art IrO2 and RuO2-based electrocatalysts. The utilization of this sprayer facilitates intimate contact with the substrate electrode and provides short ion diffusion paths, facilitating efficient electron transport. Additionally, the doping of Na ions into the Co3O4 structure results in structural distortion and charge redistribution, leading to the generation of oxygen vacancies (OVs). These OVs enhance the activity of lattice oxygen atoms, thus enabling rapid and durable oxygen evolution in an acidic media (0.5 M H2SO4). The optimal Na-Co3O4 (AA) exhibits a notably low overpotential of 360 mV@10 mA·cm−2 and at least 200 h stability. In addition, density functional theory (DFT) calculations confirm that the incorporation of Na ions significantly elevates electrical conductivity by decreasing the energy band gap and reduces the free energy barrier for the conversion of *O to *OOH, thereby improving the intrinsic OER activity. Finally, by implanting the catalyst in a single-cell proton exchange membrane water electrolyzer (PEMWE), the current density of 100 mA·cm−2 is achieved at a voltage of 1.62 V. This innovative non-noble metal catalyst holds great potential for scalable PEMWE anodes.

Effects of nitrogen vacancy sites of oxynitride support on the catalytic activity for ammonia decomposition

Nitrogen-containing compounds such as imides and amides have been reported as efficient materials that promote ammonia decomposition over nonnoble metal catalysts. However, these compounds decompose in an air atmosphere and become inactive, which leads to difficulty in handling. Here, we focused on perovskite oxynitrides as air-stable and efficient supports for ammonia decomposition catalysts. Ni-loaded oxynitrides exhibited 2.5–18 times greater catalytic activity than did the corresponding oxide-supported Ni catalysts, even without noticeable differences in the Ni particle size and surface area of the supports. The catalytic performance of the Ni-loaded oxynitrides is well correlated with the nitrogen desorption temperature during N2 temperature-programmed desorption, which suggests that the lattice nitrogen in the oxynitride support rather than the Ni surface is the active site for ammonia decomposition. Furthermore, NH3 temperature-programmed surface reactions and density functional theory (DFT) calculations revealed that NH3 molecules are preferentially adsorbed on the nitrogen vacancy sites on the support surface rather than on the Ni surface. Thus, the ammonia decomposition reaction is facilitated by a vacancy-mediated reaction mechanism.

Stoichiometric-Ratio-Controlled Fe and Ni Non-noble Metal Catalysts Supported on γ-Al2O3 for Turquoise Hydrogen and Carbon Nanotubes Production.

Herein, we synthesized a series of catalysts comprising iron (Fe), and nickel (Ni) supported on γ-Al2O3 nanopowder (Fe-Ni/γ-Al2O3) by controlling the stoichiometric ratio of the metals through the facile co-precipitation method. The ratio of Fe and Ni on the γ-Al2O3 support varied from 0 to 70 weight percent (wt%). The freshly prepared catalysts' phase, structure, and crystallinity exhibited variability as the Fe and Ni stoichiometric ratios were altered. The catalyst demonstrated effective performance in methane cracking, producing turquoise hydrogen and carbon nanotubes (CNTs) using a temperature-programmed reactor coupled with mass spectrometry. It was observed that the Fe3Ni4 catalyst, comprising 30% Fe and 40% Ni, exhibited a maximum methane conversion rate of 85% and a hydrogen yield of 72.55%. Moreover, the values of turnover frequency (2.38 min-1) indicated that the Fe3Ni4 had a better production rate and was consistent with the conversion process throughout the reaction. The structural attributes of the spent catalysts were examined, revealing variations in the lateral length, uniformity, and diameters (~33 to 56 nm) of the produced Carbon Nanotubes (CNTs) when transitioning from catalyst Fe0Ni7 to Fe7Ni0. The investigation underscored the significance of metal stoichiometrically controlled catalysts and their catalytic efficacy in methane cracking applications.

Molten Salt-Assisted Synthesis of Ferric Oxide/M-N-C Nanosheet Electrocatalysts for Efficient Oxygen Reduction Reaction.

Efficient, stable, and low-cost oxygen reduction catalysts are the key to the large-scale application of metal-air batteries. Herein, high-dispersive Fe2O3 nanoparticles (NPs) with abundant oxygen vacancies uniformly are anchored on lignin-derived metal-nitrogen-carbon (M-N-C) hierarchical porous nanosheets as efficient oxygen reduction reaction (ORR) catalysts (Fe2O3/M-N-C, M═Cu, Mn, W, Mo) based on a general and economical KCl molten salt-assisted method. The combination of Fe with the highly electronegative O induces charge redistribution through the Fe-O-M structure, thereby reducing the adsorption energy of oxygen-containing substances. The coupling effect of Fe2O3 NPs with M-N-C expedites the catalytic activity toward ORR by promoting proton generation on Fe2O3 and transfer to M-N-C. Experimental and theoretical calculation further revealed the remarkable electronic structure evolution of the metal site during the ORR process, where the emission density and local magnetic moment of the metal atoms change continuously throughout their reaction. The unique layered porous structure and highly active M-N4 sites resulted in the excellent ORR activity of Fe2O3/Cu-N-C with the onset potential of 0.977V, which is superior to Pt/C. This study offers a feasible strategy for the preparation of non-noble metal catalysts and provides a new comprehension of the catalytic mechanism of M-N-C catalysts.

Cation induced electrostatic adsorption driven self-assembly sandwich-like α-MnO2/MXene for efficient self-heating photothermal synergistic catalytic decomposition of carcinogenic gaseous formaldehyde

Realizing self-assembly between different nanoparticles is an important strategy for constructing novel nanostructures or excellent functional composites. Formaldehyde is the primary gaseous pollutant in indoor air, and achieving its ambient temperature decomposition is of great significance for improving indoor air quality. This research reports an electrostatic adsorption driven self-assembly strategy, constructing a sandwich structure α-MnO2/MXene for self-heating photothermal synergistic catalytic decomposition of formaldehyde. The self-assembly process and electrostatic adsorption driven mechanism were detailed. A comparative study was conducted on the performance and mechanisms of the self-assembled sandwich structure and mechanically mixed α-MnO2/MXene in the self-heating photothermal catalytic decomposition of formaldehyde. The sandwich structure α-MnO2/MXene with built-in electric field and Schottky barrier exhibited excellent self-heating photothermal catalytic activity for formaldehyde decomposition, realizing the 100% mineralization of formaldehyde under simulated solar-light irradiation at room temperature; even with the irradiation of visible light, the sandwich structure α-MnO2/MXene can still maintain 82.6% HCHO conversion. Furthermore, we elucidated the self-heating photothermal catalytic mechanism, shedding light on the distinct roles and contributions of photocatalysis and thermal catalysis. It was found that the photothermal catalytic mechanism of the sandwich structure α-MnO2/MXene-S composite involved a thermally assisted photocatalytic process. The advantages of the self-assembled sandwich structure and its mechanism for enhancing photothermal performance were fully revealed. This study reports an effective strategy for electrostatic adsorption self-assembly, offering a fresh perspective on developing non-noble metal catalysts for ambient-temperature formaldehyde decomposition

CeO2-conjugated CoFe layered double oxides as efficient non-noble metal catalysts for NH3-decomposition enabling carbon-free hydrogen production

CeO2-conjugated Co1.5Fe1.5 LDOs were synthesized through a one-pot co-precipitation method of Ce-introduced Co1.5Fe1.5 LDHs and their thermal treatment. By manipulating the stoichiometric molar ratio of Ce/(Co + Fe), a series of Cex-Co1.5Fe1.5 LDOs (x = 0.05, 0.1. 0.2, 0.5, and 1, corresponding to the molar ratio for the sum of Co and Fe) was comprehensively characterized to investigate the intricate interplay among factors such as spinel mixed metal oxides, LDH-derived LDOs, and the introduced Ce to achieve high catalytic performance in NH3 decomposition. Notably, Ce0.2-Co1.5Fe1.5 LDOs exhibited remarkable activity, achieving an NH3 conversion of 81.9 % at 450 °C and a WHSV of 6,000 mLNH3 gcat-1h−1, and maintained excellent NH3-conversion with a negligible decrease over 80 h of continuous operation at 550 °C and high WHSV of 30,000 mLNH3 gcat-1h−1. The synergistic interaction between the incorporated CeO2 and Co1.5Fe1.5 LDOs induced modifications of structural properties including the distribution of Co and Fe within the spinel crystal structure, as well as affecting the lattice parameters and electronic properties. These modifications play a pivotal role in ultimately altering metal-N binding energy, which facilitates the efficient activation of absorbed NH3 at the lowest temperature and minimizes the delay in recombinative N2-desorption. Hence, this study aims to highlight a new concept and demonstrate its feasibility for fabricating cost-effective and high-performing catalysts at mild temperatures to meet the growing demand for NH3 as a hydrogen carrier.

Bifunctional heterostructured nitrogen-doped carbon-layer-loaded NiSe2-FeSe2 electrocatalyst for efficient water splitting

Developing high-performance, eco-friendly bifunctional electrocatalysts is crucial to popularizing water electrolysis for hydrogen production, but it still presents major challenges. Here, we develop a composite material with NiSe2-FeSe2 heterostructure loaded on N-doped carbon layers by utilizing the metal-organic framework as a sacrificial template (NiSe2-FeSe2/NC). According to microstructural studies, direct contact between NiSe2 and FeSe2 induces charge transfer and enhances conductivity, while sensible arraying of NiSe2-FeSe2/NC nanosheets fully exposes active sites and protects catalysts from violent reaction processes. The NiSe2-FeSe2/NC heterostructured catalysts show excellent bifunctional catalytic activity for hydrogen and oxygen evolution reactions, with overpotentials of 54 and 232 mV at 10 mA cm−2, respectively. Moreover, NiSe2-FeSe2/NC also retains superiority in a two-electrode system, needing lower voltage to drive the overall water splitting at 10 mA cm−2 (1.53 V) than Pt/C||RuO2 as well as long-term stability. This work introduces a novel concept for developing state-of-the-art non-noble metal catalysts for hydrogen production and new insights into interface engineering.

Highly catalytic performance for the selective C–H bond oxidation of p-chlorotoluene over Co, Cr co-doped OMS-2 catalyst

Using O2 as an oxidant, developing a non-noble metal catalyst for the selective catalytic C–H bond oxidation of p-chlorotoluene is desirable and challenging. In this work, a series of Co, Cr co-doped OMS-2 (Octahedral Molecular Sieve-2) catalysts were prepared by a conventional refluxing method. It was found that the incorporation of Co and Cr improved the catalytic activity for the selective oxidation of p-chlorotoluene to p-chlorobenzaldehyde. Among these catalysts, CoCr/OMS-2 (Co: Cr = 1: 1, mass ratio), the best catalyst, shows that the conversion and the selectivity of p-chlorobenzaldehyde is 94.8 % and 94.3 %, respectively. The enhanced catalytic activity was due to the larger specific surface area and even dispersion of active components. The characterization results also disclosed that the co-doping of Co and Cr increased the oxygen vacancy and enhanced the ability to activate the surface lattice oxygen. Additionally, density functional theory calculations demonstrated that co-doping of Co and Cr promoted the adsorption of p-chlorotoluene and O2, and decreased the energy barrier of rate-determining step (the conversion of p-chlorobenzyl alcohol to p-chlorobenzaldehyde). Besides, when H2O was added to the reaction system as the second solvent, the activation and dissociation of O2, and the formation of p-chlorobenzaldehyde were facilitated, in agreement with the experimental results. This work demonstrated the promotional effect of Co, Cr co-doped into OMS-2 catalyst and the role of H2O for the selective oxidation of p-chlorotoluene.

Synergistic effects of MXene support and cobalt salts in dye-sensitized photocatalytic hydrogen generation

This study introduces an approach to photocatalytic hydrogen production through a dye-sensitized photocatalytic system employing MXene (Ti3C2Tx) and a non-noble cobalt metal catalyst. It was demonstrated that simple integration of eosin Y, Ti3C2Tx and cobalt salt (CoSO4) significantly enhances the photocatalytic hydrogen evolution, outperforming the corresponding system that does not include Ti3C2Tx. The key to this enhanced performance lies in the unique properties of MXene material, which facilitates effective electron transfer and acts as a support for dye and catalyst. The successful well-dispersed decoration of small (2–3 nm) cobalt-based nanoparticles on the Ti3C2Tx sheet via in situ photodeposition was confirmed by transmission electron microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The optimal hydrogen production rates were achieved with a Co to Ti3C2Tx mass ratio of 15%. This optimized interaction results in a hydrogen evolution rate of 40.1 mmol h−1 g−1 and an apparent quantum efficiency (AQE) of 35.4% at 505 nm. These findings highlight the potential of Ti3C2Tx as a versatile component in photocatalytic systems, particularly effective when paired with economically viable, earth-abundant catalysts like cobalt.

Iron-Catalyzed C-H Arylphosphorylation of Quinoxalines.

A one-pot strategy for iron-catalyzed C2,3-H arylphosphorylation of electron-deficient quinoxalines with phosphines and aryl compounds is reported. The proposed method features the use of non-noble metal catalysts, the capacity of utilizing multiple aryl compounds as substrates, the simultaneous formation of C-P and C-C bonds in one pot, the simplicity of its operation, the mildness of the reaction conditions, and its compatibility with a wide range of substrates. Moreover, it offers a practical route for direct access to 2-aryl-3-phosphino N-heteroarenes, a class of potential cyclometalated C^N and N^P bidentate ligands that are difficult to prepare with existing C(sp2)-H functionalization methods.

Catalysis of oxygen reduction reaction by iron porphyrin and its sensing application

Hemin, or iron porphyrin, serves as a non-noble metal catalyst for the oxygen reduction reaction (ORR). The stability of hemin is maintained in high salt concentrations, functioning as an ORR redox catalyst in the aqueous phase. Hemin facilitates the development of an oxygen sensor that transitions the ORR mechanism from a 2-electron to a more efficient 4-electron process. This sensor demonstrates excellent reproducibility (RSD<5%), with a wide linear range of 38.9–613 μM, a sensitivity of 0.136 ± 0.003 μA μM−1, and a limit of detection (3SB/m) of 11.8 μM.

Boosting oxygen reduction performance by copper-iron co-doped on ZIF-derived N-doped carbon nanotubes

Developing high-efficiency non-noble metal catalysts for the oxygen reduction reaction (ORR) is paramount for sustainable energy conversion. In this study, we proposed a Cu, Fe co-doped zeolite imidazole framework (ZIF)-derived nitrogen-doped carbon nanotubes catalyst (Cu–Fe@CNTs/NC) obtained by hydrothermal method and pyrolysis. The electrochemical results showed that Cu–Fe@CNTs/NC exhibited favorable oxygen reduction performance and good stability under alkaline electrolyte. The incorporation of Cu and Fe bimetallic dopants promoted the carbon nanotubes growth on ZIF nanosheets, and the collaborative action of Cu and Fe enhanced its ORR catalytic activity. These findings provide an innovative way to prepare high active non-platinum ORR catalysts.

Insights into the Synergistic Catalytic Effect of TiO2 Supported V-W Oxides for Selective C-H Bond Oxidation of Cyclohexane to KA Oil.

It is urgent to develop an efficient and stable non-noble metal catalyst for selective C-H bond oxidation of cyclohexane. Herein, a series of V-W oxides supported on TiO2catalysts (V-W/TiO2) were fabricated. The V-W/TiO2catalysts exhibited much higher catalytic activity for the selective oxidation of cyclohexane to KA oil, compared to that of V/TiO2and W/TiO2catalysts. The good distribution of active metals and the synergistic effect were responsible for the enhanced catalytic activity. H2-TPR results disclosed that the presence of V inV-W/TiO2 affected the reducibility of W6+species, and XPS verified that an electronic interaction was formed between them. Such results led to good catalytic reusability of V-W/TiO2catalyst during the reactions, and no obvious activity loss was found after six runs. The reaction mechanism was investigated, and the results verified that hydroxyl radicals generated from H2O2homolysis were the main active oxidative species. Theoretical study revealed that V dopant could regulate electronic structure of adjacent O atom, facilitating the adsorption of cyclohexane, and lower energy was needed for the rate-limiting step over V-W/TiO2during the whole oxidation reaction. This work developed an efficient V-W/TiO2catalyst for the selective oxidation of cyclohexane via a synergistic effect.