The development of efficient cobalt-based oxygen evolution catalysts is hindered by sluggish kinetics and limited lattice oxygen (OL) activation in conventional systems. A critical challenge lies in mediating the transition of adsorbed OH intermediates to activate OL oxidation, which is inherently restricted by strong Co-O covalency and high energy barriers. We address this issue by constructing a Co-CoO Schottky heterojunction within a nitrogendoped carbon matrix through molten salt-confined pyrolysis of ZIF-67. This unique architecture drives *OH migration from Co2+ sites to adjacent OL, enabled by interfacial charge redistribution across the Schottky junction. The catalyst achieves an ultralow overpotential of 270 mV at 10 mA cm- 2 and a Tafel slope of 69.4 mV dec-1, surpassing commercial IrO2 and state-of-the-art Co-based systems. In situ Raman spectroscopy and 18O isotope labeling coupled with differential electrochemical mass spectrometry confirm unambiguous OL participation in O-O bond formation via the lattice oxygen mechanism. Density functional theory reveals a stepwise *OH adsorption-migration pathway on compressively strained Co2+-OL sites, arising from the core-shell lattice mismatch, with an energy barrier of 2.15 eV, facilitated by charge redistribution-induced D-band center modulation and weakened Co-O covalency. This work establishes intermediate-mediated *OH migration in Co/CoO Schottky heterostructures as a key descriptor and a pivotal strategy to bypass conventional adsorption-energy scaling limitations, unlocking efficient OL oxidation for advanced energy conversion technologies.

High-entropy alloys (HEAs) show great promise for the hydrogen evolution reaction (HER) due to their tunable electronic structures and strong structural stability. However, most reported HEAs rely on kinetically stabilized structures, which limit the regulation of atomic and electronic structures in HEAs. In this work, a thermodynamically stabilized and driven synthesis method was employed to synthesize HEAs containing 5-15 elements. Structural characterization reveals that all samples adopt a single-phase solid solution structure, with the HEA nanoparticles (NPs) uniformly dispersed on the carbon support surface. Electrochemical tests showed that the catalytic performance of HEAs with the same elements in the HER can be tuned easily by adjusting the parameters in thermal synthesis. This provides a promising and practical pathway toward achieving "infinite" catalytic performance with "finite" metal elements. Furthermore, HEA NPs containing more than 15 types of elements can also be easily prepared. Using the HER as a model reaction, the HER catalytic activity shows regular changes with heat-treatment temperature, heat-treatment time and the number of constituent elements, indicating that the atomic coordination structure, electronic energy levels, etc., in HEAs can be continuously tuned through heat treatment synthesis parameters. For HEAs synthesized via thermodynamic routes with simple elemental mixing, the minimum overpotential for the HER can reach 32 mV, demonstrating that the thermodynamically stability-driven HEA strategy features convenience and universality in HEA synthesis and activity regulation.

The practical deployment of rechargeable zinc–air batteries (ZABs) is limited by sluggish multielectron oxygen electrocatalysis and interfacial degradation at Zn anodes. Electronic structure engineering (ESE) offers a route to tune intermediate adsorption, lower reaction barriers, and improve electrode stability at the atomic level. In this review, we summarize the mechanistic basis of ESE in ZABs, including d-band centre modulation, spin-state regulation, orbital hybridization, and charge redistribution. We then discuss recent design strategies based on isolated single-atom sites, heterojunctions, and high-entropy alloys. Beyond the air cathode, we highlight how ESE can influence Zn deposition behaviour and electrolyte solvation structures, thereby linking catalyst design to device-level performance. We also examine how density functional theory and advanced operando characterization can help resolve dynamic structural evolution under working conditions. Finally, we outline future opportunities in AI-assisted materials discovery, operando mechanism tracking, and multiscale engineering. These directions may help connect atomic-level electronic modulation with practical ZAB design and scalable device implementation.

Titanium-containing zeolites have attracted much attention because their framework titanium species as Lewis acid sites can activate green oxidants of hydrogen peroxide. This unique property enables their application in environmentally-benign oxidation processes. Among them, titanium-containing MWW-type zeolites with a unique layered structure have attracted great attention. The direct hydrothermal synthesis of Ti-MWW zeolites usually requires boric acid as an auxiliary crystallization agent. This boric acid-assisted method had adverse influence on the microenvironment of Ti active sites. The synthesis of boron-free and titanium-rich Ti-MWW remains very meaningful and challenging. Here, an effective strategy was reported to prepare titanium-rich, boron-free Ti-MWW zeolite catalysts by using low-volatility and stable Ti(SO4)2/H2SO4 acid solution to posttreat uncalcined pure-silica MWW-type zeolitic precursors (so-called ITQ-1 precursors). This strategy can effectively suppress the formation of extra-framework titanium species, which is usually formed in the Ti-MWW zeolites synthesized by traditional methods. In addition, the introduction of titanium species can be controlled by altering the structure and morphology of the precursors. It was proven that reducing the size of ITQ-1 precursors by increasing the rotation speeds during synthetic processes could promote the content of inserted Ti species by post-synthesis treatment. Ti-MWW zeolites with a more than 3.7 mol.% Ti content were achieved, most of which were tetrahedrally-coordinated framework titanium species composed of both closed-site and open-site titanium species. As far as we know, this content was the highest amounts to introduce titanium species into pure-silica ITQ-1 precursors. Due to the high content of framework Ti species, Ti-MWW catalyst showed high catalytic performance in alkene epoxidation.

The incorporation of sp-hybridized nitrogen arisen from graphdiyne (GDY) into the catalyst structure significantly improves the electrocatalytic efficiency of zinc-air batteries by modulating the electronic properties of the active sites, thereby accelerating reaction kinetics and enhancing conductivity. This work highlights the efficacy of the Co-N-GDY catalyst, where sp-N moieties in GDY serving as anchoring centers for cobalt species, which demonstrates exceptional performance in the oxygen reduction reaction, achieving a half-wave potential of 0.85 V, along with high oxygen evolution reaction performance that surpasses that of commercial Pt/C + IrO2-based batteries. The Co-N-GDY catalyst also exhibits commendable cycling stability with minimal fluctuation in voltage difference, indicating its suitability for practical applications in advanced energy storage systems. These findings underscore the importance of developing cost-effective and durable M-N-C catalysts to enhance the commercial viability and sustainability of zinc-air battery technology.

ABSTRACT The development of efficient, stable, and earth‐abundant electrocatalysts is critical for advancing electrochemical water splitting as a sustainable hydrogen production technology. Among non‐precious candidates, cobalt‐based materials have garnered significant attention due to their structural versatility and tunable electronic properties. This review comprehensively examines recent progress in cobalt‐based catalysts for the hydrogen and oxygen evolution reactions. We discuss key optimization strategies, including nanostructuring, heteroatom doping, and defect/interface engineering, that enhance activity and stability by increasing active site density, improving conductivity, and optimizing intermediate adsorption energetics. A particular focus is placed on the dynamic reconstruction of pre‐catalysts into active (oxy)hydroxide phases under operational conditions, a crucial consideration for rational design. By integrating mechanistic insights from advanced in situ characterization and theoretical calculations, we elucidate structure‐activity relationships and reaction pathways. Finally, we outline persistent challenges and future directions, emphasizing the need for standardized evaluation and the design of durable catalysts capable of operating at industrial‐scale current densities to bridge the gap between laboratory research and practical application.

The electrocatalytic two electron oxygen reduction reaction (2e- ORR) is a promising approach to produce H2O2 in acidic media. However, the high cost of precious metal-based electrocatalysts and the challenge to prepare single atom catalysts with well-defined periodic structures and large metal mass content hinder their potential industrial application. We report a carbon supported bimetallic alloy nanocatalyst by dispersing CoNi alloy nanoparticles on the surface of nitrogen-doped mesoporous hollow carbon nanospheres (CoNi/N-MHCS). The CoNi/N-MHCS exhibited a superior 2e- ORR performance with an H2O2 selectivity of 81 % and productivity of 6.048 mol gcat- 1 h- 1 in the acidic media. The catalyst also demonstrates an excellent electro-Fenton performance in degrading tetracycline hydrochloride (TCH) as a demonstration of its on-site practicability. Experiments and DFT theoretical calculations demonstrate that the charge redistribution between Co and Ni atoms due to the formation of CoNi alloy nanoparticles may reduce the reaction energy barrier of *OOH into H2O2, promote the reaction kinetics and modulate the adsorption energy of the intermediate *OOH on the CoNi active sites, thus enhancing the 2e- ORR electrocatalytic performance. This work provides new insights into the development of high efficiency carbon supported bimetallic alloy catalysts for electrocatalytic conversion of O2 into H2O2.

The efficient oxidation of p-cresol to p-hydroxybenzaldehyde (p-HBA) under base-free conditions is a significant challenge in industry. We supposed that the sluggish kinetic problems due to the lack of hydroxide ions (OH-) may be addressed if reactive oxygen species (ROS, such as H2O2, O2center dot-, 1O2, HO etc.) are introduced. Over optimized active sites in catalysts, molecular oxygen (O2) can be adsorbed and activated into nucleophilic ROS and facilitate the oxidation of p-cresol to p-HBA under base-free conditions. Herein, an ordered intermetallic PtFe nano-catalyst supported over active carbon (PtFe/C) and a supported Pd catalyst over S doped carbon (Pd/S-C) with varied size from a single atom catalyst (SAC) to ca. 5.58 nm nanoparticles (NPs) were developed and employed in aerobic oxidation of p-cresol into p-HBA. The highest p-HBA yield up to >99% was obtained over PtFe/C and Pd/S-C combined catalysts, much higher than literature reported results. Radical quenching experiments and EPR spectroscopy confirmed that singlet oxygen (1O2), superoxide radicals (O2center dot-), and hydroxyl radicals (HO) participated in the reaction path. Based on experimental data, a new catalytic mechanism for aerobic oxidation of p-cresol into p-HBA, involving ROS, was proposed. In this mechanism, Pd/S-C and PtFe/C catalysts played key roles in O2 adsorption, activation, and ROS transformation and synergistically facilitated the oxidation of p-cresol to p-HBA.

Hierarchically porous zeolites with both macroporous/mesoporous and microporous channels have received significant attention due to their better catalytic performance than that of conventional zeolites. Here, for the first time, a template with hydrolysable groups that can achieve in-situ regulation of the pH value has been designed. Employing this novel template, core-shell hierarchically porous ZSM-5 zeolites with Al-rich shells were one-step synthesized, which exhibit better catalytic activity and selectivity than conventional microporous zeolites in bulky-molecule catalysis.

One-dimensional semiconductor nanorods have shown intrinsic advantages in photocatalytic H2 evolution systems. However, the hole transfer and the subsequent oxidation reaction have been regarded as the rate-determining steps of the reaction. The introduction of only one single activity site per photocatalyst has great advantages for multi-electron reactions. Here, the ZnSe/CdS nanotetrapods (NTPs) with type-II band alignment are proposed and well designed. ZnSe is located at the center of the nanotetrapods, and its valence band is more negative than that of the CdS nanoarms. Therefore, the photogenerated holes of the four CdS nanoarms delocalize into a ZnSe core, and the electrons still reside in the nanoarms. The spatial separation of the photogenerated charges and accumulated holes accelerate the hole migration to the surface and the subsequent oxidation reaction. The ZnSe/CdS NTPs exhibit extraordinary photocatalytic H2 evolution activity and stability. Specifically, a total of 8573.5 +/- 249.0 mu mol of H2 gas is generated within 100 h of irradiation, giving the turnover number of (1.71 +/- 0.05) x 108 per ZnSe/CdS NTP. The spatial separation of photogenerated charges and accumulated holes in ZnSe core accelerates hole migration to the surface and the subsequent oxidation reaction, resulting in the exceptional photocatalytic performance of ZnSe/CdS nanotetrapods.

The arsine-protected cluster [Au 13 (AsPh 3 ) 8 Cl 4 ] + holds greater potential to enable a better trade-off between catalytic stability and activity, whilst it is also surface reactive and suitable for further derivatization by ligand exchange.

Hierarchically porous zeolites are a type of very hot catalyst with improved catalytic performances as compared with conventional microporous-only zeolites due to the improved mass transportation among the hierarchical meso/macropores, which are expected to be the next-generation catalysts for conversion of bulky molecules and/ or polymers. Moreover, hierarchical zeolites with the single crystalline structure that is an identical registry of micropores within the entire particle identified the less pore blockage and less diffusion limitation compared to an aggregated structure of nano-zeolites. The developed synthetic methods were mostly conducted in a liquidphase system and usually required expensive additives, such as silanes or mesoporogons, etc. Finding facile and cost-effective synthetic methods have been still challenging. Here, a facile and cost-effective strategy by controlling the growth/crystallization in a solidified hydrogel system was reported for the synthesis of Ticontaining MFI-type zeolites (TS-1) to simultaneously achieve hierarchical porosity, single-crystalline structure, and high catalytic performance in alkene oxidations. The synthesized zeolites were characterized by XRD, SEM, TEM, Nitrogen adsorption analysis, DRUV spectroscopy, IR spectroscopy, etc. The growth processes were also tracked and well-characterized. It was found that the solid-phase transformation mechanism was dominated for forming the hierarchical structure. This strategy could directly produce TS-1 with abundant intracrystalline continuous mesopores and large amounts of active framework titanium species, contributing to higher activity for epoxidation of alkenes compared to the traditional microporous-only TS-1 zeolites.

Hollow-structured mesoporous silica has wide applications in catalysis and drug delivery due to its high surface area, large hollow space, and short diffusion mesochannels. However, the synthesis of hollow structures usually requires sacrificial templates, leading to increased production costs and environmental problems. Here, for the first time, amino-functionalized mesoporous silica hollow spheres were synthesized by using CO2 gaseous bubbles as templates. The assembly of anionic surfactants, co-structure directing agents, and inorganic silica precursors around CO2 bubbles formed the mesoporous silica shells. The hollow silica spheres, 200–400 nm in size with 20–30 nm spherical shell thickness, had abundant amine groups on the surface of the mesopores, indicating excellent applications for CO2 capture, Knoevenagel condensation reaction, and the controlled release of Drugs.

Hierarchical zeolites have attracted great attention due to the integration of mesopores and/or macropores into the microporous crystalline framework, which decreases the steric and diffusional limitations in the small-size micropores of zeolites. Among them, single-crystalline hierarchical zeolites are much desirable due to fewer crystalline defects, higher mechanical stability, and less blocking of the uniform direction of microporous channels, which show high catalytic performance in conventional industrially-important small-molecule reactions, and heavy-oil catalytic cracking, biomass catalytic conversion, polymer degradation, etc. Here, a novel one-pot kinetics-dominated strategy was developed to synthesize titanium-containing single-crystalline hierarchical zeolites via synergy of polyelectrolytes and framework hetero-atoms by means of concentrating the starting precursor, restriction of the Oswald ripening to protect nano-crystals, as well as oriented attachment between nano-crystals. The resultant zeolite displayed a much higher catalytic performance in olefin epoxidation and cyclohexanone ammoximation than those of conventional pure-microporous zeolites.

Open-pore MFI zeolite nanosheets were prepared by removal of organic structure-directing agents (OSDA) from a multilamellar MFI zeolite (ML-MFI) using a mixture of 95%similar to 98%(w/w)H2SO4 and 30%(w/w)H2O2 with V-H2SO4:V-H2O2=3:1 (known as piranha solution), followed by ultrasonication for exfoliation and sedimentation for purification. The exfoliated MFI zeolite nanosheets were characterized by various techniques, such as X-ray diffraction (XRD), scanning electron microscope (SEM), transmittance electron microscope (TEM), N-2 adsorption-desorption, Fourier transform infrared spectrometer (FT-IR) and thermal gravimetric analyzer (TGA), etc., indicating that OSDA was removed after the piranha solution treatment and dispersed, open-pore MFI nanosheets were obtained followed by exfoliation through ultrasonication. Continuous MFI nanosheet membranes were prepared by depositing the open-pore MFI nanosheets on home-made alumina disc supports by a simple vacuum assisted filtration method. Single gas permeance tests on the MFI zeolite nanosheet membranes indicated that ideal selectivities for n-butane over i-butane of 4.1 similar to 5.8 with a permeance of n-butane of 2.2x10(-7)similar to 4.1x10(-7) mol . m(-2).s(-1).pa(-1) were achieved.

Assisted by an anionic polyelectrolyte of poly(acrylic acid) (PAA), high-performance titanium silicalite-1 (TS-1) could be facilely synthesized at very low usage of expensive organic templates (tetrapropylammonium hydroxide). The presence of PAA helped to incorporate more active Ti species into the TS-1 framework and change the morphology to a plate-like shape, which was beneficial to molecular diffusion among its micropores to access the Ti active sites. Therefore, TS-1 synthesized with PAA showed much higher catalytic activity than that synthesized using the traditional synthesis without polyelectrolytes, and only a 30% usage amount of organic template was used. Moreover, this ultra-cheap catalyst also displayed a better catalytic activity than commercial TS-1 synthesized via a series of complicated preparation processes including alkene epoxidation with hydrogen peroxide as a green oxidant.

Introduction of titanium into the frameworks of 14-ring extra-large-pore zeolites with CIT-5 (CFI-type, 7.2 x 7.5 angstrom) and SSZ-53 (SFH-type, 6.4 x 8.7 angstrom) topology has successfully been conducted by a chemical vapor deposition (CVD) method. The prepared titanosilicate zeolites have been characterized by XRD, SEM, UV-vis spectroscopy, IR spectroscopy, N-2 adsorption, and elemental analysis. According to the characterization data, titanium is mostly incorporated into the framework of the zeolite in a tetrahedrally coordinated state. The catalytic epoxidation of cycloalkenes with H2O2 and tert-butyl hydroperoxide (TBHP) has been measured. The prepared titanosilicates with extra-large pores show superior performances for bulky molecule oxidation using TBHP as an oxidant compared to medium-pore TS-1 and large-pore Ti-beta.

Hierarchical Sn-β zeolites were synthesized for the first time without using an organic structure directing agent.

Titanosilicate molecular sieve (TS-1) is an important commercial catalyst for green production of oxy-functionalized chemicals such as alcohols, ketones, epoxides, and oximes. Active TS-1 can normally be achieved in the synthetic media strictly free of alkali metal cations (e.g., Na+ and K+). This condition severely raises the purity demands of starting reagents, which greatly increases the production cost. Herein, we developed a method to achieve highly active titanosilicates in the presence of high concentration alkali metal cations using anionic polymer-based quasi-neutral media. This synthetic route could effectively inhibit the adverse influence of alkali metal cations on the incorporation of active titanium(IV) sites into the framework of titanosilicate, directly affording the maximal framework titanium content (2.0 wt.%) with almost 100% yield. This development shows a great commercial potential and opens the possibility of preparing silica-based molecular sieves/zeolites in non-fluoride neutral media. (C) 2016 Elsevier Inc. All rights reserved.

Titanium(IV) incorporated into the framework of molecular sieves can be used as a highly active and sustainable catalyst for the oxidation of industrially important organic molecules. Unfortunately, the current process for the incorporation of titanium(IV) requires a large amount of expensive organic molecules used as organic-structure-directing agents (OSDAs), and this significantly increases the production costs and causes environmental problems owing to the removal of OSDAs by pyrolysis. Herein, an OSDA-free process was developed to incorporate titanium(IV) into BEA-type molecular sieves for the first time. More importantly, the hydrophobic environment and the robust, 3 D, and large pore structure of the titanium(IV)-incorporated molecular sieves fabricated from the OSDA-free process created a catalyst that was extremely active and selective for the epoxidation of bulky cyclooctene in comparison to Ti-incorporated BEA-type molecular sieves synthesized with OSDAs and commercial titanosilicate TS-1.