The dynamic structural cycling of oxygen vacancy (Ov) is widely recognized as crucial in determining catalytic behavior.However, current research predominantly focuses on the static structural properties of Ov (e.g., Ov...

Precise control over the metal-support interfacial structure plays a critical role in enhancing the activity and selectivity of iron-based catalysts for syngas conversion. Using silicon nitride as the starting precursor of silicon support, a series of SiNxOy supports with different oxidation degree were constructed via controlled oxidation under air, enabling modulation of the Fe-Si interfacial environment. A systematic comparison between silicon nitride-derived supports and conventional silica support revealed significant differences in structural evolution and catalytic behavior of iron catalysts. Spectroscopic characterizations including FTIR, solid-state NMR, XPS, XRD, and Mössbauer spectroscopy demonstrated that the unique interfacial structure formed during the oxidation of Si3N4 stabilizes the active iron species (carbides) and suppresses the formation of undesired phases (Fe3O4), thereby reducing CO2 selectivity. These findings underscore the critical influence of support precursors on interfacial chemistry and reaction pathways, providing new insights and strategies for the rational design of Fe-based catalysts.

Although olefin aromatization reactions offer a potential route for the high-value utilization of Fischer-Tropsch naphtha, their industrial implementation is hindered by challenges such as coke-induced deactivation and the formation of large amounts of low-value alkane by-products. In this work, a series of Ga(x%)-EATP-550 catalysts were prepared via equal-volume impregnation of Ga onto an acid-etched attapulgite (EATP) support, followed by calcination at 550 degrees C. The catalysts were evaluated for the aromatization of olefins. The results show that the reaction proceeds mainly through direct dehydrogenative aromatization, yielding approximately 65% aromatics, while generating short-chain olefins (about 20% yield) as the main by-products. This system effectively suppresses the formation of long-chain aromatics and low-value alkanes, presenting a promising technical pathway for upgrading Fischer-Tropsch naphtha.

For supported metal catalysts, the support either disperse the active phase or modulate the electronic properties of active metals to regulate the catalytic activity and selectivity. This work focuses on the electronic effect of supports in Fischer-Tropsch synthesis (FTS) by using Fe, Fe/MgO, Fe/MnO, Fe/Si3N4, and Fe/SiO2 catalysts. The different supports were selected according to Sanderson's electronegativity equilibrium principle. It is found that the electron density of iron and the CO adsorption strength are enhanced with the decrease of the support electronegativity. Furthermore, FTS results show that, except for the Si3N4 support, the selectivity towards heavy hydrocarbons and carbon dioxide gradually increases as the electronegativity of the supports decreases, while the selectivity towards light hydrocarbons decreases. The Fe/Si3N4 catalyst exhibits the lowest CO2 and the highest heavy hydrocarbon selectivity among all the catalysts. This work provides us with a fundamental understanding of the electron-donating or accepting effect of support materials in the FTS reaction.

Deep hydrogenation of polycyclic aromatic hydrocarbons (PAHs) into jet fuel is an important strategy for the upgrading of light cycle oil (LCO). Zeolite-supported metal catalysts have exhibited good catalytic performance for hydrogenation of PAHs under relatively mild conditions. However, the impacts of acidity variations in zeolite supports, arising from the differences in framework Al (Al-F) distribution on the catalytic behavior of zeolite-supported metal catalysts in the deep hydrogenation of PAHs remains unclear. Herein, two series of mesoporous ZSM-5 samples, that is ZSM-5-E-x and ZSM-5-F-x, with the differences in Al-F distribution but similar Si/Al ratios, were prepared in the crystallization system with or without NaOH. The results of NH3-TPD, Pyridine-IR, N-2 adsorption-desorption and SEM reveal that two series of HZSM-5 samples have similar acid density and acid strength, textural properties, morphology and particle size. However, the results of XPS, Al-27 MAS NMR, 2,6-Ditert-butylpyridine-IR, catalytic cracking of 1,3,5-triisopropylbenzene and the controlled reactions as well as DFT calculation indicate that the higher enrichment degree of Al-F on the external surface and the suitable arrangement mode of Al-F in ten-membered ring (10-MR) of HZSM-5-F-x compared to HZSM-5-E-x in case of the similar Si/Al ratios, result in Pt/HZSM-5-F-x exhibiting remarkably-improved deep hydrogenation performance of phenanthrene (PHE) compared to Pt/HZSM-5-E-x. Particularly, the selectivity to perhydrophenanthrene (PHP) over Pt/HZSM-5-F-50 can reach above 99.0% at a conversion of PHE (>99.0%). Furthermore, Pt/HZSM-5-F-50 exhibits well reusability. This work helps to clarify the impact of Al-F distribution in ZSM-5 on catalytic hydrogenation performance for PAHs, providing valuable guidance for design and development of efficient catalysts for the hydrogenation of PAHs. (c) 2025 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY-NC-ND license

Understanding the structure-property relationship is of pivotal importance for the rational design of efficient solid catalysts yet persists as a significant challenge due to the inherent complexity of solid materials. Here, we present an efficient strategy to decipher the interfacial catalysis in metal-oxide nanocatalysts during CO2 hydrogenation through synergistically integrated experimental and theoretical investigations with machine learning (ML) algorithms. Using model Pd/CeO2 catalysts as a proof-of-concept system, the matched experimental and ML-predicted results demonstrate that given sufficient oxygen vacancy concentrations on the support matrix the catalytic performance is primarily governed by the nature of supported metals. Specifically, atomically dispersed Pd species exhibit exceptional intrinsic activity for CO production, which is attributed to its enhanced H spillover and hydrogenation capacities but weakened CO binding affinity. Further ML analysis indicates the sum surface d charge of supported metal as the principal factor governing catalytic performance among four types of typical intrinsic features influencing catalytic hydrogenation processes, which could be directly evaluated by a geometric descriptor of average coordination number of the metal on the support, associated with the metal particle size. This work provides a generalizable theoretical framework for understanding metal-oxide interfaces in CO2 hydrogenation and opens up a novel approach for catalytically fundamental studies to unravel the complex nature of heterogeneous catalysis.

The efficient conversion of C9 heavy aromatics into high-value benzene, toluene, and xylenes (BTX) products is essential for optimizing petroleum refining. This process often depends on both diffusion and the unresolved relationship among structure, acidity, and reactivity of zeolite catalysts. This study focuses on the intracrystalline micro-/meso-pores in ZSM-5 and decouples the interdependent effects of crystalline morphology and Al distribution of Brønsted acid sites (BAS) in ZSM-5 on C9 aromatic conversion pathways. The hierarchical ZSM-5 catalysts have the identical SiO2/Al2O3 ratios (SAR) and the different distribution of framework Al-species. This dominates the acid distribution of the zeolites and catalytic performances of the catalysts in C9 aromatic reaction. In toluene/trimethylbenzene (TMB) transalkylation, the hierarchical porosity coupled with reduced crystallite size of the ZSM-5 enhances 1,2,4-TMB conversion by 24.4% and xylene selectivity by 17.9% versus conventional microporous ZSM-5. The product distribution is positively correlated to the concentration of Al atoms localized at channel intersections of the ZSM-5. Diffusion-decoupled experiments demonstrated acid site spatial configuration in the ZSM-5 governs the reaction pathway selection, with aluminum enrichment at channel intersections favoring transalkylation over disproportionation. The hierarchical ZSM-5 in submicron with intracrystalline mesopores and enriched intersection-channel aluminum favors transalkylation of C9 aromatics to BTX. The hierarchical ZSM-5, with submicron crystallites, intracrystalline mesopores, and enriched intersection-channel aluminum, enhances transalkylation of C9 aromatics to BTX.

Direct Z-scheme photocatalytic systems based on SnC/As2S3, SnC/As2S2Se, and SnC/As2SSe2 van der Waals heterostructures are systematically investigated using density functional theory. Comprehensive analyses are conducted on structural stability, electronic and optical properties, strain-modulated solar-to-hydrogen (STH) efficiency, and the Gibbs free energies of hydrogen and oxygen evolution reactions (HER/OER). Notably, the SnC-based heterostructures exhibit high STH efficiencies, reaching up to 36.93 % under 4 % biaxial tensile strain. Nonadiabatic molecular dynamics (NAMD) simulations reveal that SnC/As2S2Se-II exhibits the lowest hole transfer, indicating enhanced oxidation activity protection for OER. SnC/As2S3-I demonstrates the fastest interlayer electron-hole (e-h) recombination time, thereby effectively facilitating the direct Z-scheme charge transfer pathway and highlighting its significant promise for efficient overall water splitting. In particular, HER and OER proceed spontaneously in SnC/As2S2Se-I and SnC/As2SSe2-I, driven by their photogenerated charge carriers, while SnC/As2S3-I and SnC/As2S2Se-II are functional within pH ranges of 5.24-14 and 3.70-11.36, respectively. These results establish a theoretical foundation for the rational design of SnC-based chalcogenide heterostructures for efficient solar-driven overall water splitting.

Understanding the structure-property relationship is of pivotal importance for the rational design of efficient solid catalysts, while this process is seriously blocked by their structural complexity. Here, we have developed a machine learning (ML) assisted strategy to deeply decouple the interfacial catalysis of metal-oxide nanocatalysts in CO2 hydrogenation by combining experimental and theoretical results with ML algorithm. Using representative Pd/CeO2 catalysts selected on basis of an experimental data-driven ML model, the matched experimental and ML-predicted results demonstrate that, besides surface oxygen vacancies of the support that are responsible for the adsorption and activation of CO2, the catalytic activity and CO selectivity are determined by the H spillover and hydrogenation properties and the binding strength of CO intermediate, respectively, both tightly relevant to the nature of supported metals. Further feature-importance analysis indicates that the d states’ center of supported metals, associated with the intrinsic nature of metal atoms and the metal-support interactions, acts as the most important factor governing the catalytic performance. This work greatly deepens the fundamental understanding of metal-oxide NCs in CO2 hydrogenation and innovatively pens up a new paradigm for catalytically fundamental studies to unravel the complex nature of heterogeneous catalysis.

Cryptochromes (CRYs) are photolyase-like blue-light/ultraviolet-A (UV-A) receptors that regulate diverse aspects of plant growth and development. Maize (Zea mays), a major crop often grown under high UV-B radiation, harbors four copies of CRY. However, whether CRYs in maize have evolved to improve UV tolerance or acquire novel functions remains unclear. In this study, CRISPR-Cas9-engineered Zmcry mutants are used to investigate the functions of ZmCRYs in maize. The findings reveal that ZmCRYs act redundantly in mediating blue light signaling and inhibiting mesocotyl elongation. Furthermore, we demonstrate that ZmCRYs mediate blue light-enhanced UV-B stress tolerance in maize by upregulating the expression of genes involved in the biosynthesis of UV-B stress tolerance-related metabolites, including phenylpropanoids, flavonoids, and fatty acids. Further analyses show that blue light modulates both the accumulation and composition of epidermal waxes, suggesting that blue light enhances epidermal wax accumulation for UV-B stress tolerance. Notably, we identify that ZmCRY1 directly interacts with GLOSSY2 (GL2), a key acyltransferase in very-long-chain fatty acid metabolism, in a blue light-strengthened manner to mediate blue light-promoted C32 aldehyde accumulation, shedding new light on the enigma of the aldehyde-forming pathway in plants. These results highlight the critical roles of ZmCRY1s in mediating blue light-regulated epidermal wax biosynthesis and UV-B tolerance in Zea mays.

Tailoring supported bimetals to alloyed or phase-separated structures is of vital importance while this process is blocked by the support interferences during universal impregnation processes. Conventional trial-and-error approaches rooted in chemical intuition often lack efficiency and generality. Here, we present a design strategy guided by the statistical sampling of comparative ease of alloy formation through the metadynamics-based gas-solid nanoreactor approach, which enables the rational and systematic development of bimetallic nanocatalysts (NCs). Using metal oxide-supported PdAu coupling with model CO2 reduction as a proof-of-concept system, the integrated theoretical and experimental results not only validated the reliability of simulation results but also successfully predicted and realized the alloy formation or phase separation of supported PdAu NCs. The generated PdAu alloys over CeO2 weaken the metallicity of supported Pd species and thus the catalytic hydrogenation property, but increase moderate basicity, contributing to activated CO2 hydrogenation to CO via a formate intermediate. However, the phase separation of Pd and Au over TiO2 support promotes formic acid production efficiency attributed to increasing weak basicity to accelerate CO2 activation during a bicarbonate pathway. These findings highlight statistical sampling as a general broadly applicable framework for the rational design of advanced bimetallic NCs.

We designed a new type of two-dimensional graphene-like carbon nitride material, g-C7N5H. Through firstprinciples calculations, the stability, electronic structure, optical properties, and photocatalytic performance of g-C7N5H were deeply explored. After confirming its good thermal stability through Ab initio molecular dynamics simulation, the band structure was calculated using PBE and the more accurate HSE06 hybrid functional method. The band gap width of this material is 3.41 eV under the HSE06 method, which may lead to limited photocatalytic activity. Further calculations of the band edge potential and light absorption spectrum showed that although g-C7N5H has the basic conditions for photocatalysis, its narrow light absorption range restricts the catalytic efficiency. By innovatively introducing the strategy of doping boron/phosphorus atoms at different sites, the band gap of the material was successfully reduced, and the visible light absorption boundary and intensity were expanded. This work not only reveals the potential application of two-dimensional graphene-like materials in photocatalysis but also opens up a new way to develop efficient solar energy conversion devices.

Background The nickel carbonylation reaction is of great significance for nickel extraction and the application of nickel-based materials. Previous studies have mostly been conducted on nickel without load. However, the ores used in industrial nickel extraction contain various oxides, and the size of nickel can affect the reaction. Ni/Al2O3 catalysts are common, and it is appropriate to study the influence of various parameters on the formation kinetics of Ni(CO)4 on them.Results Temperature, pressure and particle size have different effects on the carbonylation reaction of Ni in Ni/Al2O3. Specifically, the reaction rate is the fastest when the temperature is 80 degrees C. Increasing pressure can rapidly accelerate the carbonylation reaction process. When the particle size is within 8.1-9.1 nm, the carbonylation reaction rate reaches the highest.Conclusion The study revealed that the carbonylation rate of Ni is accelerated significantly with the increase of temperature and pressure. Through the in-depth analysis of the first derivative of Ni conversion of the model sample, it is found that the reaction process of Ni with CO can be clearly divided into two stages: the first stage occurs quickly due to a large number of highly active Ni atoms contacting with CO; the second stage is accompanied by the increase of internal defects, cracks and grooves in Ni particles, and these structural changes make more Ni sites exposed. In addition, small size of Ni exhibited higher initial activity than large size of Ni, but could have a lower reaction degree after sufficient reaction time. (c) 2025 Society of Chemical Industry (SCI).

In this paper, based on first principles, density functional theory is used to investigate the doping of transition metal atoms (Mn, Fe, Co, Ni) in AlN/SiC nanoribbons with edge passivation by different atoms (Cl, F, H, O) to induce magnetism and modulate properties. The research results show that the new structures proposed in this study with doping of transition metal atoms induce magnetism and a transition of properties. First, calculations determined the ferromagnetic coupling state to be the most stable state of the initial magnetic structure. Then, band structures, the density of states, and charge densities were analyzed to investigate the transition of properties. The AlN/SiC nanoribbons with Ni doping in Cl, F, and H atom edge-passivated structures all transitioned to half-metallic properties. Half-metal properties appeared in the AlN/SiC nanoribbons with Fe and Co doping in O atom edge-passivated structures, enabling the generation of 100% spin-polarised current at the Fermi level. In addition, other structures exhibited properties of narrow bandgap semiconductors and metals. Furthermore, we used molecular dynamics simulations to verify the stability of the structures, demonstrating that the structures proposed in this study can stably exist. This provides more ideas and potential applications for the development of spintronics devices.

Fe基催化剂是费托合成反应的常用催化剂,然而费托过程中的高水分压容易导致催化剂活性相氧化失活,因此及时将生成的水从催化剂表面移除,是防止活性相氧化、进而延长催化剂使用寿命的关键。本工作将疏水剂多孔聚二乙烯基苯与催化剂Fe 2 N物理混合,利用多孔聚二乙烯基苯的疏水性,加速了水的迁移过程。此策略有效平衡催化剂表面水分吸附与释放,减少水分对活性位点的占据,促进合成气高效转化。未添加多孔疏水剂的Fe 2 N在费托反应中,CO转化率仅为34.8%,且反应后存在活性相被氧化的现象;而添加了多孔疏水剂的F e2 N,其CO转化率高达80.2%,同时反应后并未观测到活性相被氧化的情况。实验结果表明,疏水性聚合物在优化催化剂微环境、提升反应效率及产物选择性方面具有优异效果,为合成气转化提供了新策略。

Two-dimensional carbon-nitrogen materials show great potential for photocatalysis, but enhancing their catalytic performance remains challenging. We design a carbon nitride 2D material composed of 10 carbon, 2 nitrogen, and 4 hydrogen atoms (g-C10N2H4). Structural stability is rigorously validated through thermodynamic (MD/formation energy), dynamic (phonon spectra), and mechanical (elastic constants) stability criteria. Through systematic investigation, we find g-C10N2H4 is a direct bandgap semiconductor with suitable electronic properties for photocatalysis. The material's band structure spans water redox potentials, and its light absorption spectrum indicates that the material can absorb part of the visible light. To improve photocatalytic performance, we develop two effective methods: (1) multilayer stacking reduces the bandgap, expanding visible-light absorption range; (2) heterojunction construction forms a Schottky barrier, significantly enhancing charge separation efficiency. These results demonstrate g-C10N2H4's promise as a photocatalyst and provide practical approaches for optimizing 2D carbon-nitrogen materials.

Exploring the restructuring mechanism of solid catalysts is of pivotal importance for the rational design of efficient catalysts, yet remains a significant challenge. Traditional chemical potential theory assumes a spatially uniform gas reservoir with a well‐defined chemical potential but neglected the spatial variations induced by surface reactions, mass transportation, and temperature gradients in the operando conditions. Here, we employ a thermodynamics‐guided strategy, integrated with experimental models initiated from distinct precursor structures, to demonstrate the structure of restructured catalyst determined by the local oxygen chemical potential ( μ O ). Using cobalt‐ceria catalyzed CO 2 hydrogenation as a proof‐of‐concept system, comprehensive characterizations reveal that supported cobalt species undergo in situ restructuring during reaction processes, either reducing oxidative cobalt species to lower oxidation states or oxidizing metallic cobalt to positive valence states, ultimately forming CoO x ensembles with Co(II) as the primary component. Starting from either metallic Co or CoO x , the resulting differences in catalytic activity modify the local atmosphere and the μ O near catalyst surface. This leads to the formation of distinct CoO x ensembles, which in turn dictate the divergent catalytic performance. These findings provide a comprehensive physical picture elucidating the intrinsic correlation between the environmental atmosphere and corresponding structure of restructured catalysts.

Ni‐based catalysts are considered to be promising candidates for moderate‐low temperature (200−400 °C) reverse water‐gas shift (MLT‐RWGS) as an important CO 2 reduction pathway. However, their high activation properties for CO inevitably lead to severe methanation at high CO 2 conversion, creating an activity‐selectivity trade‐off and unsatisfactory CO yields. Here, a novel supported Ni‐based catalyst is deveolped, consisting of abundant Ni δ+ atoms anchored in situ on ultrathin Ni‐phyllosilicate nanosheet (a‐Ni δ+ −PSNS(400), 0< δ ≤1). The a‐Ni δ+ −PSNS(400) break activity‐selectivity trade‐off and achieve high CO selectivity (92%) toward at a formation rate of 21.0 mmol CO h −1 gcat −1 , outdistancing those of all prevailing Ni‐based catalysts for MLT‐RWGS. Such catalytic performance is attributed to unique geometric/electronic effects of a‐Ni δ+ −PSNS(400), i.e., exposed monodisperse Ni δ+ atoms with low electron density on ultrathin Ni‐phyllosilicate nanosheet. The ultrathin nanosheet enables anchored Ni δ+ atoms to fully expose and disperse, boosting atom‐utilization efficiency and atom‐synergistic effects, endowing them with high catalytic activity; while low electron density of Ni δ+ atoms extremely weakens their chemical adsorption of CO, preventing further CO hydrogenation into CH 4 , which ensures their high CO selectivity. This work provides new insights into the design of active microstructures of high‐performance Ni‐based catalysts for synchronous high activity‐selectivity.

This paper constructs CdO/Al2SSe heterojunctions. The first-principles method is used to study its stability, electronic structure, optical properties, and the improvement of photocatalytic performance. First, 12 CdO/ Al2SSe van der Waals heterojunctions were constructed, and after calculating the binding energy, the two stacking modes with the lowest binding energy were selected for the subsequent calculations. The band structure of heterojunction is calculated by the HSE06 hybrid functional method. By calculating the projected band and work function, the heterojunction forms a Type-II heterojunction. The pH value of the system is adjusted to neutral, and the redox potential is overall shifted upward compared to pH = 0 under acidic conditions, making the band edge position of the heterojunction more conducive to the photocatalytic water decomposition reaction. In order to further optimize the photocatalytic performance of the material, external strain was applied to the heterojunction. The light absorption range of the heterojunction is expanded after applying moderate strain. Based on the study of HER, the results show that heterojunction exhibits good catalytic performance in photocatalytic water splitting and has a significant improvement in hydrogen production efficiency, which shows broad application prospects in the field of photocatalytic water splitting and clean energy production.