We disclose a sustainable, additive-free strategy for the synthesis of 2-arylbenzimidazoles using a cost-efficient Fe2O3-based heterogeneous catalyst. This one-pot cascade reaction, employing benzyl alcohols and o-nitroanilines as substrates, proceeds efficiently under mild conditions. Remarkably, the amorphous Fe2O3-200 catalyst delivers dramatically enhanced catalytic performance over its crystalline analogues, affording benzimidazole products in up to 99% yield. Mechanistic investigations attribute this superior activity to the high density of oxygen vacancies and the strong adsorption affinity for benzyl alcohol, which collectively promote the key dehydrogenation step. The catalyst also exhibits outstanding stability, maintaining its high reactivity over five consecutive cycles without a noticeable loss of activity, thereby highlighting its promise for practical and scalable applications.

Hybrid double-atom catalysts (HDACs) provide a versatile platform to steer the carbon monoxide reduction reaction (CORR) toward C2 products. However, the underlying principles connecting atomic-site electronics, electrolyte microenvironments and selectivity remain unclear. This work develops a mechanistic picture for carbon nitride (CN)-supported HDACs composed of 3d-metal and p-block-element dual centers by integrating density functional theory (DFT), ab initio molecular dynamics (AIMD), constant-potential simulations, and interpretable machine learning. Screening 36 HDACs identified stable dual centers with continuously tunable CO binding, which is governed by the d/p-band centers, metal-carbon bonding and adsorption-induced charge transfer. Mechanistic and constant-potential analyses reveal an intermediate dimer-strength regime and an operating window of around -0.4 V vs. RHE, where C-C coupling and proton-coupled electron transfer (PCET) kinetics are optimally aligned on NiB@CN. Explicit electrolyte modeling further shows that cation hydration, interfacial hydrogen-bond networks, and water orientation influence the balance between early *CO hydrogenation and *CO dimerization, with K+ giving the most favorable conditions among the modeled cations under the present computational conditions. Finally, an interpretable model built on ΔG *CO, the metal-carbon bond length, and a quantitative charge-transfer metric captures the descriptor-activity trend within the present HDAC dataset and serves as a preliminary prescreening aid within this chemical space.

ABSTRACT Designing reducible metal oxide catalysts that remain stable under hydrogenation conditions represents a longstanding challenge in heterogeneous catalysis, as most oxides are readily reduced and structurally degraded in H 2 ‐rich environments. Here, we report an oxygen‐anchoring strategy that enables hydrogen‐tolerant metal oxide catalysts. Using this approach, a CuO/TiO 2 catalyst stabilized by an oxygen‐rich C─O framework (HT‐CuO/TiO 2 ) was constructed for the selective hydrogenation‐coupling of nitriles to secondary amines. The oxygen functionalities within the C─O framework act as anchoring sites that stabilize CuO nanoclusters and suppress their reduction under hydrogen. The stabilized CuO nanoclusters function both as hydrogen activation centers and Lewis acid sites for nitrile adsorption. Meanwhile, the introduction of TiO 2 leads to the formation of intimate CuO─TiO 2 interfacial structures, accompanied by the presence of Ti 3+ species and enhanced hydrogen activation behavior. Notably, this hydrogen‐tolerant behavior extends to a range of reducible metal oxides, including CuO, Cu 2 O, CoO, and NiO, demonstrating the generality of the oxygen‐anchoring stabilization principle. This work establishes a general strategy for stabilizing reducible metal oxides under hydrogen and unlocks their catalytic potential for hydrogenation chemistry.

The creation of diverse heterogeneous interfaces is a key strategy for developing highly efficient electrocatalysts for the alkaline oxygen evolution reaction (OER). This paper reports an easy two-step synthesis of a trimetallic (NiCoFe) sulfide catalyst with a 0D-2D hybrid structure via a competitive co-deposition strategy. Unlike conventional hydrothermal or coprecipitation methods, this strategy enables the simultaneous formation of 0D nanoparticles and 2D nanosheets on carbon nanotubes (CNTs), achieving uniform dispersion and robust anchoring of the 0D nanoparticles on the 2D nanosheets, forming abundant and stable heterogeneous interfaces. This effectively prevents the agglomeration of 0D nanoparticles. Coupled with CNTs, an efficient electron transport network is established, significantly enhancing local charge transfer efficiency and intrinsic catalytic activity. The resulting catalyst exhibits an exceptionally low overpotential of 260 mV at 100 mA cm-2 for the OER in alkaline media. When employed in an anion exchange membrane water electrolyzer (AEMWE), it demonstrates remarkable durability, operating stably for over 500 h at a high current density of 65 °C, 100 mA cm-2 in 1 M KOH without performance decay. Using X-ray absorption fine structure (XAFS) spectroscopy, we demonstrated the electronic coupling mechanism at the interface between CNTs and the ternary metal sulfide. This work highlights the critical role of interface engineering and co-deposition competitive strategy in applications and preparation of 0D-2D sulfide catalysts, but also provides new insights into the rational design of advanced non-precious metal electrocatalysts.

Electron transfer process (ETP) represents an efficient and robust pathway in peroxymonosulfate (PMS) activation, yet its practical application is limited by sluggish kinetics, inefficient electron transport, and constrained catalyst suitability. Herein, we design a roselike Ce-doped Co3O4 catalyst (RL Ce-Co3O4) with electron-deficient Co sites to enable efficient PMS activation by a selective ETP pathway in spinel oxide. Atomic-level Ce incorporation in Co3O4 induces electron delocalization of octahedral cobalt (CoOh) via 3d-2p-4f coupling orbital, constructing electron-deficient CoOh active sites with depopulated 3d orbitals. The roselike architecture improves the accessibility of active sites to further promote the reaction kinetics. Mechanistic insight reveals that the electron-deficient CoOh sites enhance the adsorption and stabilization towards both PMS and bisphenol A (BPA) by intensified Co-O covalent interactions. Meanwhile, Ce doping improves the electrical conductivity of Co3O4, promoting rapid electron transfer from BPA to PMS* via a catalyst bridge, thereby disrupting the conventional Co2+/Co3+ redox cycling and establishing a catalyst-mediated ETP pathway. Synergistically, RL Ce-Co3O4 exhibits superior performance, achieving 99.9

The hydrogenation of nitriles holds significant academic and industrial relevance, yet achieving controllable selectivity remains challenging due to the involvement of multiple reaction intermediates. In this study, we developed a heterogeneous Ni/diatomite-500 catalyst featuring dual Ni0-Ni2+ active sites, enabling precise regulation of the product distribution between primary amine and secondary amine. Structural characterizations and mechanistic investigations reveal that Ni0 efficiently activates H2, driving a hydrogenation-condensation-hydrogenation pathway to yield Secondary Amines. In contrast, Ni2+ facilitates the adsorption of ammonia and the intermediate (E)-N-benzylidene-1-phenylmethanamine, steering the reaction toward a hydrogenation-condensation-ammonolysis pathway for selective primary amines formation. Moreover, Ni/diatomite-500 demonstrates a broad substrate scope, effectively converting 37 nitriles into primary amines and 14 into secondary amines, including structurally challenging heterocyclic and long-chain aliphatic nitriles. Moreover, Ni/diatomite-500 maintains stability and recyclability. This work achieves the selective synthesis of primary and secondary amines in a non-noble metal catalytic system, offering a sustainable and efficient amines production route.

The one-pot direct synthesis of secondary amines from nitro compounds and alcohols is ideal, but remains limited by the need for excess alcohols and additives. In this work, we report the simple preparation of a multifunctional Cu/Nb2O5 catalyst that efficiently catalyzes nitro reduction, alcohol dehydrogenation, aldehyde-amine coupling, and imine hydrogenation. In contrast, Nb2O5 supported with other metals fails to meet these requirements. Mechanistic studies reveal that the abundant acidic sites on Nb2O5 promote efficient hydroxyl adsorption and benzyl alcohol dehydrogenation, while the introduced Cu species synergistically facilitate the hydrogenation of nitro and imine intermediates. Moreover, the catalyst exhibits excellent recyclability, a broad substrate scope, and promising scalability in enlarged reactions. This study presents a novel catalytic strategy for the green synthesis of secondary amines from nitro compounds and alcohols under equimolar condition.

The selective cleavage and functionalization of inert C(OH)-C bonds are critical steps in the valorization of renewable biomass into high-value chemicals. However, current catalytic strategies often rely on metal-based additives or harsh conditions. Herein, we report a recyclable, metal-free catalytic system composed of selenium nanoparticles supported on nitrogen-doped carbon nanosheets (SeNPs@CNs), which enables the aerobic oxidative cleavage of C(OH)-C bonds to esters and amides under mild, additive-free conditions. The catalyst exhibits broad substrate compatibility-including sterically hindered aryl alcohols and beta-O-4 lignin model compounds-and maintains activity on the gram scale. Mechanistic control and characterization studies reveal that selenium nanoparticles, rather than atomically dispersed Se species, are responsible for the observed activity due to their more favorable substrate adsorption and oxygen activation properties. This work establishes selenium nanostructures as an environmentally benign and mechanistically distinct platform that complements existing transition-metal systems for sustainable organic synthesis.

Metallic foams hold significant promise as lightweight structural materials. However, most conventional metallic foams are inherently rigid and brittle, frequently undergoing structural collapse. There is an urgent demand to develop cost-effective, facile-to-synthesize metallic foams with enhanced flexibility. Herein, it is discovered that diethanolamine solvent, a multifunctional organic solvent, not only reduces Ni2+ ions but also induces the assembly of generated Ni0 units into 3D metallic nickel (Ni-BPHs) sponges. In addition, the optimization of the binary solvent ratio combined with an acetic acid-assisted method is demonstrated to markedly accelerate the reaction kinetics, concomitant with significantly enhance the coordination density of organic ligands on metallic nickel surface. This approach enables the synthesis of metallic nickel (Ni-BNSs) sponges with enhanced flexibility. The Ni-BPHs and Ni-BNSs as electrocatalysts that exhibit efficient activity and stability for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media. The solvent-ligand-mediated reduction and induced assembly strategy has also been demonstrated by extending to other similar ligands. This work marks an important advance in metallic nickel foams and provides a promising strategy for synthesizing mechanically flexible metallic sponges.

Efficient photocatalysts rely on constructing heterostructure with reasonable configuration. In this study, a novel conjugated polymer with a D-pi-A structure was fabricated from polycondensation of perylene diimide and dibenzothiophene sulfone through the suzuki coupling reaction, during which the biphenyl was incorporated as a it-bridge. The photocatalytic hydrogen evolution performance of these copolymers were optimized by introducing different mass fractions of it-bridges via adjusting the additions of biphenyls The optimized PyBpDBSO-5 copolymer, with 17 wt.% perylene diimide and 5 wt% biphenyl, obtained photocatalytic hydrogen productivity of 48.54mmol/h g- 1 under visible light without adding Pt as cocatalyst, which is 146.1 % improvement compared to the poly(dibenzothiophene-S,S-dioxide) (PDBTSO, 19.72mmol/h g- 1). Based on the analysis of physical and chemical properties, electrochemical testing, the significant advantages of D-pi-A configuration in promoting light absorption, photogenerated carriers transfer and separation was confirmed, which was further rationalized by the larger co-planarity of the polymer based on DFT calculations. This study provides inspiration about construction of conjugated organic polymer catalyst towards efficient photocatalysts.

Traditional sulfoxide synthesis often relies on toxic oxidants and harsh conditions. Photocatalytic oxidation using inorganic semiconductors provides a greener approach but is limited by low catalytic efficiency. Herein, we developed a heterostructure catalyst enriched with cadmium vacancies (denoted as Cd v S x /Ti 3 CN). The optimized Cd v S 4 /Ti 3 CN exhibited a high sulfoxide production rate of 21.85 mmol·g cat –1 ·h –1 , outperforming most reported catalytic systems. Comprehensive characterization revealed that sulfur dosage was precisely tuned during synthesis to generate abundant cadmium vacancies and expose active crystal facets. In particular, the presence of cadmium vacancies enhances substrate adsorption via unsaturated coordination sites, lowers the energy barrier for bond activation, and promotes the activation of O 2 into superoxide radicals. Moreover, Ti 3 CN further facilitates photogenerated electron transfer and enhances superoxide radical concentration by enabling favorable band alignment with CdS. In addition, the catalyst demonstrates excellent substrate compatibility and recyclability. This work offers a new approach for improving the performance of CdS‐based inorganic semiconductor catalysts in sulfoxide synthesis through Cd defect engineering.

The accumulation of depleted uranium (DU), a byproduct of nuclear energy production, poses significant environmental concerns. Converting DU into functional catalysts represents a promising strategy for its resource valorization. Herein, we report a U-238-based catalyst, UO4 center dot 2H(2)O, with negligible radioactivity, synthesized from DUF6-derived alpha-U3O8 via a dissolution-precipitation method, enabling selective oxidation of aniline to nitrosobenzene, azobenzene, and azoxybenzene by solvent tuning. Structural and mechanistic studies reveal that surface defects form frustrated Lewis pairs (FLPs). Its Lewis acidic U6+ sites strengthen the U=O bond and shorten its length, enhancing electron-withdrawing ability and promoting aniline adsorption, while the basic oxygen-vacancy sites facilitate H2O2 activation and singlet oxygen generation, thereby promoting aniline oxidation. Notably, the catalyst is regenerable via calcination-reprecipitation for up to 60 cycles, with an E-factor well below the fine chemical benchmark. This work provides a scalable strategy for DU valorization and a practical platform for the synthesis of nitrogen-containing fine chemicals.

Lignin and other underutilized biomass resources have significant potential for producing specific chemicals through hydrogenation. However, current challenges in this field include not only the high cost of catalyst preparation but also the demanding reaction conditions required. In this study, a CoNi-NC alloy catalyst with high specific surface area and mesoporous structure was prepared by calcining Ni-doped ZIF-67 material. The Co3Ni1-NC catalyst achieved complete conversion of guaiacol with a cyclohexanol yield reaching 92.7 %, under conditions of 1.2 MPa H2 pressure and 180 degrees C reaction temperature. The study found that Co-Ni alloys possess superior hydrogen adsorption activation capability, which is a critical factor affecting the hydrogenation capacity of the catalyst. The prepared Co3Ni1-NC not only significantly reduces the H2 pressure and temperature for the guaiacol hydrodeoxygenation (HDO) reaction but also achieves high-efficiency conversion of guaiacol in water as the primary solvent. This undoubtedly saves costs and reduces environmental impact. The CoNi-NC catalyst also possesses magnetic properties, making it easy to fully recover. Related characterization and cycling experiments have demonstrated that the catalyst has excellent recyclability. These properties of the CoNiNC catalyst will significantly enhance its economic viability. Furthermore, this catalyst exhibited excellent hydrogenation performance for lignin model compounds, providing a valuable reference for the application of alloy MOFs materials in the hydrogenation of lignin compounds.

The one-pot synthesis of amines from benzyl alcohol (BA) and nitrobenzene (NB) represents a step-economic method. However, reported works typically require more than 3 equiv of BA to complete the transfer hydrogenation of NB, and few studies can achieve selective synthesis of imines and secondary amines. In our previous work, Zr(OH)4 demonstrated both hydrogenation and dehydrogenation capabilities. Building on this, another component Cu was introduced to enhance its catalytic performance for catalyzing coupling reaction between stoichiometric BA and NB under a H2 atmosphere. The physical hybrid catalyst Cu + Zr(OH)4 selectively produced imines, while the supported catalyst Cu/Zr(OH)4 yielded secondary amines. Characterization and mechanism experiments revealed that modulating the proximity between Cu and Zr(OH)4 leads to (1) different adsorption abilities of the catalyst for N-benzylideneaniline (NBA) and (2) interactions between Zr(OH)4 and Cu in close contact, which stabilized the electronic structure of Cu forming more Cu+/Cu0 ion pairs with strong H2 activation ability. This work presents a catalyst design strategy and offers an approach for the selective preparation of N-benzylideneaniline and N-benzylaniline.

Utilizing single atom sites doping into metal oxides to modulate their intrinsic active sites, achieving precise selectivity control in complex organic reactions, is a highly desirable yet challenging endeavor. Meanwhile, identifying the active site also represents a significant obstacle, primarily due to the intricate electronic environment of single atom site doped metal oxide. Herein, a single atom Cu doped TiO2 catalyst (Cu1-TiO2) is prepared via a simple “colloid-acid treatment” strategy, which switches aniline oxidation selectivity of TiO2 from azoxybenzene to nitrosobenzene, without using additives or changing solvent, while other metal or nonmetal doped TiO2 did not possess. Comprehensive mechanistic investigations and DFT calculations unveil that Ti-O active site is responsible for triggering the aniline to form a new PhNOH intermediate, two PhNOH condense to azoxybenzene over TiO2 catalyst. As for Cu1-TiO2, the charge-specific distribution between the isolated Cu and TiO2 generates unique Cu1-O-Ti hybridization structure with nine catalytic active sites, eight of them make PhNOH take place spontaneous dissociation to produce nitrosobenzene. This work not only unveils a new mechanistic pathway featuring the PhNOH intermediate in aniline oxidation for the first time but also presents a novel approach for constructing single-atom doped metal oxides and exploring their intricate active sites.

Developing a green, stable, and cost-effective heterogeneous catalyst and clarifying its catalytic mechanism for the selective oxidation of C-H bonds without solvent to carbonyl compounds hold a significant theoretical and practical value. Herein, we synthesize perovskite catalysts using the sol-gel method to catalyze the selective oxidation of ethylbenzene. Notably, La0.4Sr0.6CoO3-800 (800 degrees C is the calcination temperature of the catalyst) demonstrates remarkable efficacy, converting 73% of ethylbenzene into acetophenone with a selectivity of 93%. Characterization analyses reveal that the incorporation of strontium moderately disrupts the internal balance of the perovskite structure, leading to increased oxygen vacancies and enhanced oxygen adsorption capacity. Moreover, electron paramagnetic resonance and mechanistic studies prove that molecular oxygen on the catalyst surface is converted to singlet oxygen (O-1(2)) and superoxide radical anions (O-center dot(2)-). The presence of O-1(2) significantly aids in the production of O-center dot(2)-, thereby effectively promoting the oxidation of ethylbenzene. This research introduces a new reactive oxygen species (ROS) transformation mechanism and provides valuable insights into the selective oxidation of hydrocarbons.

The exploration and design of highly active, low-cost, transition metal-based electrocatalysts are crucial for large-scale green hydrogen production. Here, the heterostructure of oxygen-coordinated cobalt single atoms with O-doped carbon and CoO nanowires (Co-O-C-O/CoO/CF) is constructed for efficient and stable HER at industrial current densities. Benefiting from the synergistic effect of O doping and CoO nanowires, Co-O-C-O/CoO/CF exhibits extremely low overpotentials of 24.8, 229, and 239 mV to achieve current densities of 10, 500, and 1000 mA cm- 2 in 1.0 M KOH solution, respectively, and operates stably for 1000 h at 1000 mA cm- 2 . Additionally, when coupled with NiFe-LDH in a self-assembled electrolyzer, it delivers a high current density of 1000 mA cm- 2 at 1.97 V, along with outstanding stability, outperforming Pt/C||NiFe-LDH and most reported electrolyzers. Density functional theory (DFT) calculations reveal that the optimized d-band center and binding strength of H* and OH* intermediates for Co-O-C-O/CoO/CF lower the energy barrier of the rate-determining step. This work provides a new pathway for engineering Co-based catalysts for green hydrogen production at industrial current densities.

Designing heterojunction hydrogen evolution photocatalysts with advanced hierarchical structures and rational compositions is crucial to achieving efficient conversion of green energy, but remains challenging. Here, a facile in situ modification strategy was developed to couple CeO2 while forming hollow NiCo-LDH nanosheets, leading to a unique NiCo-LDH/CeO2 nanosheet heterostructure catalyst with enhanced photocatalytic hydrogen production performance. Through experiments and dynamic simulations, the reaction process was deeply studied, confirming the formation of heterojunction rather than doped products. Surprisingly, thanks to the advantages of a hollow lamellar architecture and the presence of interfacial interactions, the hydrogen production rate of dye-sensitized NiCo-LDH/CeO2 nanosheets under visible light irradiation reaches 4312 mu mol h(-1) g(-1), which is twice as much as that of NiCo-LDH nanosheets. Meanwhile, the Ni sites in the NiCo-LDH/CeO2 heterojunction having a smaller Gibbs free energy may act as active centers. The current work provides new insights into the rational design and construction of efficient heterojunction catalysts with hierarchical structures.

Sulfoxides, a class of pharmaceuticals and fine chemicals of significant importance, are readily peroxidized to sulfones in the H2O2 system. Altering the intermediate oxygen species is the key to achieving selectivity regulation. Herein, Zr(OH)4 was used to support Mo species, after calcining at 500 degrees C, obtaining a unique amorphous composite oxide with Mo uniformly dispersed in the ZrO2 matrix (MoaZr0.8Ox-500). MoaZr0.8Ox-500 demonstrates enhanced catalytic proficiency, enabling the synthesis of sulfoxides within 30 minutes at 30 degrees C. Reactive oxygen species (ROS) quenching experiments and EPR spectra indicate that MoaZr0.8Ox-500 possesses the ability to rapidly and directly participate in the heterolytic cleavage of H2O2 to produce 1O2 without passing through the intermediate (center dot)O2-, preventing the peroxidation of sulfoxides to sulfones. Additionally, the prevalence of basic sites in MoaZr0.8Ox-500 is conducive to proton transfer, which plays a significant role in the heterolytic cleavage of H2O2. Furthermore, MoaZr0.8Ox-500 exhibits excellent reproducibility, scalability, and broad substrate applicability. This study provides new insights into the selective regulation of the sulfide oxidation reaction, as well as the preparation of amorphous solid solution.