The petroleum refining industry faces increasing challenges in processing sulfur-rich crude oils while meeting stringent environmental regulations. Increasing the metal loading is the most straightforward approach to enhancing catalyst activity. However, under high metal loading conditions, the catalyst tends to form a significant amount of isolated low-activity NiSx and NiOx species. This study presents an effective " sulfidationoxidation-secondary sulfidation" reconstruction process to enhance the hydrogenation performance of high-loading sulfide NiMoW/SiO2 catalysts. The migration of active species on the metal surface was induced through high-temperature calcination and sulfur-oxygen transformation processes, leading to the conversion of isolated NiSx and NiOx species into a distinctive NiMoWS/NiSx-SiO2 composite active phase, with NiSx functioning as a secondary support. Extensive characterization using XRD, HRTEM-EDS, XPS, and DFT calculations revealed that this structural modification substantially increased metal dispersion, sulfidation degree, and hydrogen spillover effects. The optimized NiMoW-300(S) catalyst displayed excellent hydrodesulfurization (HDS) activity and hydrogenation selectivity, with a relative volumetric activity (RVA) 2.49 times higher than that of the conventional NiMo/gamma-Al2O3 catalyst, while also demonstrating outstanding stability.

The design of catalytic systems integrating high activity and selectivity is pivotal for achieving the dual objectives of efficient CO2 conversion and clean energy production. Herein, this study systematically investigated the core properties and modulation mechanisms of graphdiyne-supported nickel transition metal atoms (Nix@GDY) toward CO2 reduction reaction (CO2RR) by using density functional theory based approach. The results demonstrate that the GDY monolayer possesses a stable two-dimensional porous architecture, which provides optimal anchoring sites for Ni atoms loading. Electronic structure analyses reveal significant electronic coupling between Ni and GDY, which enhances charge transfer efficiency and facilitates the adsorption and activation of CO2. For the Nix@GDY system, Ni1-3@GDY systems maintain excellent structural stability, whereas Ni4@GDY suffers from structural distortion. Notably, Ni1-3@GDY catalysts exhibit distinctly different CO2RR catalytic behaviors. Specifically, Ni1@GDY can reduce CO2 to HCOOH with a limiting potential (UL) of-0.53 V. Ni2@GDY demonstrates superior bifunctional catalytic activity, enabling spontaneous CO2 conversion to both CO (Path I, UL =-0.32 V) and HCOOH (Path II, UL =-0.41 V). Ni2@GDY can catalyze CO2 to CO with a UL of-0.32 V. In contrast, Ni3@GDY predominantly undergoes HER. The divergent CO2RR performance of Ni1-3@GDY is closely related to their electronic interactions with the adsorbed *COOH and *OCHO intermediates. Beyond providing theoretical guidance for the experimental development of high-efficiency CO2RR catalysts, this study establishes a robust NiX@GDY catalytic system and elucidates the regulatory mechanism of Ni loading density on CO2RR performance.

Micro silicon (mSi) is a promising anode candidate for all-solid-state batteries due to its high specific capacity, low side reactions, and high tap density. However, silicon suffers from its poor electronic and ionic conductivity, which is particularly severe on a micro scale and in solid-state systems, leading to increased polarization and inferior electrochemical performance. Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions. However, achieving effective, uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers. Therefore, current doping research is primarily limited to nanosilicon. In this study, we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium (Ge) in the mSi substrate. The Joule-heating process activated the mSi substrate, resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping. Surprisingly, the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity (70 times). Meanwhile, the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling. Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells. This work provides substantial insights into the rational structural design of mSi alloyed anode materials, paving the way for the development of high-performance solid-state Li-ion batteries.

Stringent environmental regulations and the need to process heavy, sour crudes are driving the development of advanced hydrodesulfurization (HDS) catalysts, particularly Ni-promoted Mo/W sulfide catalysts. Although the promotional role of Ni in sulfide HDS catalysts is well recognized, the origin of activity suppression under Ni-rich conditions remains unclear. In this work, a series of high-loading NiMoW/SiO2 catalysts with varying Ni contents were investigated to clarify why further Ni addition leads to activity suppression in the HDS reaction under Ni-rich conditions. Combined Py-IR, EPR, Raman, XPS, and DFT analysis reveal that the key factor is the balance between -SH and coordinatively unsaturated sites (CUS) on the sulfide surface. An appropriate Ni content increases the abundance of catalytically effective sites while maintaining favorable -SH/CUS matching, leading to the highest HDS activity for Ni1Mo1W1. In contrast, excess Ni causes a continuous increase in the relative abundance of -SH species without a corresponding effective generation of additional CUS sites, thereby disrupting the -SH/CUS balance and suppressing DBT conversion. The optimized Ni1Mo1W1 catalyst also exhibited stable performance over five cycles and a 1.47-fold higher relative volume activity than the industrial NiMo/γ-Al2O3 reference catalyst (8 MPa, 300 °C), and good stability during a 360 h real-oil hydrotreating test. This work identifies -SH/CUS imbalance as a major origin of activity suppression under Ni-rich conditions in NiMoW catalysts.

This review systematically elaborates the recent advancements in high-entropy alloys, high-entropy oxides, high-entropy sulfides, and other high-entropy materials for CO 2 reduction via photocatalytic, electrocatalytic, and thermocatalytic pathways.

Biomimetic photocatalysis inspired by nitrogenase is a promising approach to nitrogen fixation. Success in this strategy relies on the multi-metal synergistic active sites and efficient charge separation. In this study, a cascaded CN/MoFeTiO S-scheme heterojunction photocatalyst was constructed by modifying a ternary MoO3/Fe2O3/TiO2 (MoFeTiO) with g-C3N4. The optimal 0.05CN/MoFeTiO achieved an outstanding ammonia production rate of 760.5 mu mol g-1 h-1, which is 2.7 and 42.5 times higher than that of individual MoFeTiO and g-C3N4, respectively, outperforming many previously reported photocatalysts. Moreover, the corresponding apparent quantum efficiency (AQY) reached 4.1 % at 450 nm, highlighting its excellent utilization of visible light. Joint experimental and theoretical studies confirm that the constructed cascaded S-scheme heterojunction efficiently separates charge carriers, while the multi-metal (Mo/Fe/Ti) sites synergistically lower the energy barriers for N---N bond activation and NH3 desorption, thereby boosting the overall nitrogen fixation efficiency. This work provides a viable paradigm for designing high-performance nitrogen-fixing photocatalysts through a strategy that integrates biomimetic multi-site design with heterojunction engineering.

This manuscript summarizes the research progress in the laser-induced preparation and application of biomass-derived carbon materials and further discusses their current challenges and development prospects.

Supported and bulk phase catalysts are both extensively used in hydrogenation reactions, possess distinct strengths and limitations. Aiming to create a catalyst that combines the benefits of both, a series of NiMoW/SiO2 catalysts were synthesized with varied metal loadings using SiO2 supports characterized by different pore structures. The catalytic activities of these catalysts were evaluated using 1-methylnaphthalene, dibenzothiophene and quinoline as model compounds. Comprehensive microstructural characterization was performed through ICP-OES, N2 physisorption, HRTEM, SEM, and XPS techniques. The investigation revealed that both the catalytic and microstructural properties of the catalysts gradually changed from the supported catalysts to the bulk catalysts with the gradual increase of the metal loadings. This transition was accompanied by a significant enhancement in activity and hydrogenation selectivity compare to the supported catalysts. Nonetheless, this catalyst preserved the benefits of a superior pore structure, straightforward preparation methods and excellent regeneration.

Lithium-ion batteries (LIBs) suffer from severe capacity degradation and shortened cycle life at low operating temperatures due to sluggish Li+ diffusion kinetics within the bulk phase of large-sized electrode materials, limiting their applicability in extreme environments. However, practical strategies to address these challenges are scarce, and a systematic understanding of low-temperature Li+ storage remains limited. In this work, we construct a grain-boundary-rich crystal structure in vanadium oxide cathode through a solid-state phase transition strategy, and reveal that both the grain boundary density and the amorphous region ratio are closely linked to low-temperature capacity retention. Unlike conventional nanoparticle agglomeration or assembly, this structure features large grains segmented into numerous nanocrystallites by amorphous regions, while preserving overall structural integrity. The loose atomic packing at the grain boundaries reduces topological constraints and introduces significant free volume within the bulk phase, thereby enhancing Li+ transport kinetics under low-temperature conditions. Additionally, lattice strain fluctuations, induced by abundant defects, effectively mitigate the volume changes during lithiation and delithiation processes by releasing local stress at the grain boundaries. As a result, the developed vanadium oxide cathode exhibits unprecedented high-rate capacity (152 mA h g-1 at 1.0C and 105 mA h g-1 at 3.3C), excellent capacity retention (72.5%), and long-term cycling stability (5000 cycles) at -40 degrees C, alongside superior performance even at lower temperatures.

One of the utmost targets for catalysis research is to meet social needs in a profitable manner. Zeolitic and "nonzeolitic components" (such as silica, alumina, amorphous aluminosilicate, clay, etc.), as indispensable constituents of an industrial catalyst, both actively participate in industrial processes like polyolefin catalytic cracking and residue fluid catalytic cracking. Yet, the main research activities focus mainly on the diffusion behaviors of a single zeolitic or nonzeolitic component. In this work, the pore interconnectivity between zeolitic and nonzeolitic components to better ensure the diffusion and migration of reaction intermediate products in between was systematically studied by adopting a series of ZSM-5@meso-SiO2 core-shell mesostructures as models to mimic industrially applied multicomponent zeolite-based catalysts with varying pore interconnectivities between the zeolitic (ZSM-5) and nonzeolitic components (meso-SiO2). Their distinctive differences in the multiscale diffusion behaviors and structure-performance relationships represent the following three summarized scenarios: (1) micro/mesopore orientation, (2) spatial distribution of components, and (3) micro/mesoporous relative pore sizes thereof. These reveal that a well-connected micro/mesopore network can effectively accelerate interfacial diffusion and fully enhance the catalytic efficiency of the zeolitic component, highlighting the foundational functions of pore interconnectivity between zeolitic and nonzeolitic components in terms of the significance of the free migration of reactant species in between.

The development of efficient and low-cost overall water splitting electrocatalysts for an anion exchange membrane (AEM) electrolyzer is desirable for hydrogen production. The control of geometric and electronic structures of electrocatalysts can improve the catalytic efficiency of hydrogen evolution reaction (HER) and durability in oxygen evolution reaction (OER). Spatially confined growth and heteroatom doping can achieve this prospect of the target electrocatalysts. Herein, we prepared a carbon-shell confined Mo-doped CoP electrocatalyst (MoCoP@C) via an anion adsorption coupled pyrolytic phosphorization method. A Metal-Organic Framework (MOF) of Co was used to achieve Mo doping and carbon-shell encapsulation. Mo doping significantly alters the electronic structure of CoP, which produces a local polarized environment for water dissociation during alkali HER process. Meanwhile, carbon-shell confines growth and provides a protective layer for durable OER process. Consequently, Mo-CoP@C exhibits attractive alkali electrocatalytic HER and OER activities with the overpotentials of 122 and 280 mV at 0.01 A cm- 2. Finally, the assembled Mo-CoP@C-CP & Vert;Mo-CoP@C-TFF AEM electrolyzer could operate for 500 h at 0.1 A cm- 2.

Carbon coating designs for microparticulate silicon (mSi) anodes are significant in stabilizing the volume change, yet their poor Li+ transport ability and brittleness during cycling lead to sluggish interfacial kinetics, making the fast-charging of mSi anode very difficult. Herein, we fabricate a mechanical-kinetic integrated coating structure with mixed carbon and lithium fluoride components for mSi anodes, which demonstrates superior interfacial Li+ transport kinetics and high-mechanical-modulus confinement to suppress the mSi pulverizations. Consequently, excellent rate capability and ultra-long cycling life (1500 cycles) are achieved in mSi-based lithium-ion batteries. Especially, this coating with low work function enables facilitated interfacial Li+ de-solvation and inorganic-rich solid electrolyte interphase formation, achieving mSi anode with a high capacity of 1359 mAh g- 1 under an ultrahigh current density of 20 A g- 1. This work provides an important coating engineering strategy for Si anodes by effectively combining superior interfacial mechanics and kinetics.

CoMo6 heteropolyacids were modified by cationic surfactants with different alkyl chain lengths to obtain oil- soluble Co-Mo complexes, which were subsequently employed to synthesize highly dispersed hydrodesulfurization catalysts. The surfactants, as structure-directing agents, markedly affected the morphology, specific surface area, and sulfurization degree of the Co-Mo sulfides at the sulfurization stage, resulting in more accessible edge active sites and Br & Oslash;nsted acid sites. Among the various Co-Mo sulfides, the one derived from dodecyl trimethyl ammonium bromide (DTAB)-modified CoMo6 heteropolyacid (DTA-CoMo-S) exhibited the highest hydrodesulfurization (HDS) reaction rate (1.1x10- 5 mol/(gcat & sdot;s)) for 4,6-dimethylbenzothiophene (4,6DMDBT) at 330 degrees C and an initial H2 pressure of 7.0 MPa. DFT confirmed that H2S adsorption and S-O exchange were more likely to occur on the surface of DTA-CoMo6 during at the sulfurization stage, which was conducive to the sulfurization of the precursor and generated more CoMoS active phases and SO 4 2- groups. These species promoted both the HDS of 4,6-DMDBT and low-temperature cracking reactions of the intermediate products. In addition, the oil-soluble DTA-CoMo6 complex showed better hydrocracking, HDS and hydrodemetallization performance in the hydrotreatment of vacuum residue.

The efficient utilization of lignin from the papermaking black liquor has attracted interest due to its carbonneutral value and industrial application. This work illustrates a simple support-phosphate-pretreatment strategy to develop superdispersed Ni species in activated carbon (AC) to enhance the hydrodeoxygenation (HDO) reactions of the lignin model compound guaiacol into biohydrocarbons under alkaline conditions. For the first time, sodium polyphosphate was applied as a pretreatment agent for coconut carbon in the synthesis of carbonsupported Ni catalysts. Superdispersed Ni nanoparticles were achieved on Ni/NaPnOAC with a particle size of 2.5 nm, which was much smaller than that on unmodified Ni/C (13.1 nm). The characterization results and reactions revealed that the P-O that formed served as anchoring sites for the Ni species and strengthened the interaction between the Ni species and support (SMSI), which resulted in significantly improved dispersion of the Ni metal sites and, thus, a nearly 6-fold greater yield of hydrocarbons was obtained on Ni/NaPnOAC (58.1 %) than on Ni/C (10.1 %). In addition, compared with Ni2P/NaPnOAC and NiS/NaPnOAC, Ni/NaPnOAC exhibited higher HDO activity, especially higher direct deoxygenation (DDO) activity and higher benzene yield, reducing hydrogen consumption during the HDO reaction.

Petroleum asphalt, characterized by its rich aromatic hydrocarbon structures and high carbonization yield, emerges as an ideal precursor for generating porous carbons intended for supercapacitors (SCs). Despite asphalt's classification into four distinct components, the intricate composition due to its diverse sources still presents an unresolved challenge when it comes to elucidating the predominant structural characteristics underlying porous carbons. In the present investigation, we adopted potassium bicarbonate (KHCO3) as a templating agent, and the potassium-containing compounds were thermally polymerized with carbon-based free radicals to facilitate the synthesis of porous carbon materials through carbonization process. We observed that the fabricated porous carbon with a substantial content of heavy fraction (68.5 wt %) demonstrated the maximal pore volume (1.02 cm3 g-1) and specific surface area (SSA) of 1229 m2 g-1, yielding in the power density of 625 W kg- 1 at the energy density of 17.88 W h kg- 1 used 1 M tetraethylammonium tetrafluoroborate in acetonitrile (TEATFB/AN). Notably, we corroborated the reliability of the entire process through a rigorous scaling-up experiment to 10 g, demonstrating entirely consistent performance. Our research introduces a novel avenue for strategically selecting petroleum asphalt precursors, with the overarching objective of producing cost-effective carbon materials endowed with commendable performance attributes.

Inducing the surface reconstruction of spinels is critical for improving the electrocatalytic oxygen evolution reaction (OER) activity. Herein, S-doped NiCo2O4 hollow cubic nanocage was synthesized by anion etching Metal-Organic Frameworks (MOFs) template and air annealing strategies. The hollow structure possesses a large specific surface area and pore size, facilitating active site exposure and mass transport. S2-doping regulates the electronic structure, reducing the oxidation potential of Ni sites during the OER process, thus promoting the surface reconstruction into gamma-NiOOH active species. Meanwhile, S2-doping enhances conductivity, accelerating interfacial charge transfer. As a result, S-NiCo2O4-6 exhibits superior OER activity (262 mV overpotential @ 10 mA cm-2) and stability in 1.0 M KOH solution. Furthermore, 20 % Pt/C||S-NiCo2O4-6 only needs 1.832 V to achieve 50 mA (the electrochemical active area is 4 cm2) in a homemade anion exchange membrane (AEM) electrolyzer. This work proposes a novel approach for preparing efficient anion-doped spinel-based OER electrocatalysts.

Manipulating the local coordination environment holds immense potential in augmenting the catalytic performance of single-atom catalysts, which remains a great challenge. Through theoretical prediction, we find the catalytic properties of atomic Co centers towards selective hydrogenation of nitroarenes can be effectively manipulated by adjusting the coordinated number of P atoms, among which Co-N2P2 configuration stands out. Accordingly, a single-atom Co1-N/P-C catalyst featuring Co-N2P2 coordination was precisely fabricated through a sacrificial P-doped g-C3N4-template strategy. The optimal electronic structure of Co-N2P2 enables favorable chemical affinities toward nitroarene and H2, promoted heterolytic dissociation of H2, and accelerated reaction kinetics. Consequently, the Co1-N/P-C catalyst exhibits outstanding catalytic activity (overall TOF of 241.5h-1), selectivity (>99%), and exceptional stability towards the hydrogenation of various functionalized nitroarenes, far surpassing other coordination configurations and most reported non-precious metal catalysts. This work deepens our understanding of the relationship between coordination structure and catalytic performance, offering boosted single-atom catalysts for selective hydrogenation of nitroarenes.

The future implementation of ultralow sulfur fuel regulations requires researchers to have an excellent understanding of the mechanism of the synergistic effect between the Co(Ni) and (Mo)W sulfides in supported Co(Ni) Mo(W)S hydrodesulfurization (HDS) catalysts. This synergistic effect occurs when the distance between two metals is on the mm or nm scale. To investigate the promotion of HDS on the mu m scale, a series of Co and Mo multilayer flake catalysts with a thickness of 1 mm were prepared by laminate molding. The distance between CoSx and MoS2 in these specially structured catalysts was adjustable on the mu m scale by controlling the order and quality of the catalyst powder. The results for the HDS of dibenzothiophene (DBT) demonstrate that there is an obvious synergistic effect between CoSx and MoS2 on the mu m scale. The results of pyridine IR spectroscopy indicate that this synergy is due to CoSx and MoS2 synergistically generating more coordinatively unsaturated sites (CUSs) and -SH active sites at the mu m scale, thus increasing the HDS activity. Moreover, the catalyst activity increases as the distance between CoSx and MoS2 decreases, and the fact that the feed comes into contact with CoSx first greatly improves the activity.

Graphene oxide (GO)-based membranes have shown considerable promise in the field of water treatment. However, the structural swelling of GO membranes in water has hindered their further development. A single regulatory approach seems difficult to simultaneously improve permeability, selectivity, and stability. In this study, we present a dual regulation strategy for GO membranes employing the 1,4-Diaminobutane crosslinker to prevent swelling and maintain an interlayer spacing of 1.34 nm, resulting in effective dye rejection, and employing the hydrophilic EMT-type zeolite promoter to improve the membrane's water permeability. The obtained NH2-GO/10EMT composite membrane exhibited enhanced pure water flux (from 9.0 to 20.8 L/m2 h bar) and anionic dye rejection (from 87.2% to 97.6%) with promising structure stability (at least 20 h), while greatly improving the membrane's fouling resistance (the water recovery ratio increased from 46.5% to 86.2%). Our findings provide a straightforward and efficient approach to the development of high-performance GO membranes for selective water separation.

Transformation of lignin-derived feedstocks into valuable hydrocarbons is of significant importance but still challenging. This work investigates the hydrodeoxygenation (HDO) of lignin compound guaiacol on Pt-based catalysts with improved surface hydrophobicity and metal dispersion for the first time. The efficiency of guaiacol hydrodeoxygenation into hydrocarbons over Nb2O5-modified Pt-based catalyst reaches 51 %, nearly doubling that over unmodified Pt/gamma-Al2O3 catalyst (25 %). On the one hand, Nb2O5 causes the decrease of hydroxyl groups on catalyst, leading to the enhanced hydrophobicity of catalysts, which increases the reaction rate of guaiacol into hydrocarbons on unit of Pt metal sites. On the other hand, Nb2O5 strengthens the metal-support interaction, which minimizes the size of Pt nanoparticles, providing more exposed metal sites, thus leading to a higher hydrocarbons yield on catalyst. However, excess introduction of Nb2O5 leads to partial coverage of Pt metal sites, resulting in decreased yield of hydrocarbons. Furthermore, the routes of guaiacol HDO reaction over modified Pt-based catalysts are investigated. This work further illustrates the influence of catalyst surface properties on the HDO process of lignin compound, and thereby provides a promising approach for adjustment of catalyst surface properties in order to promote water-liberated reactions.