Efficient hydrogen activation and spillover remain critical challenges limiting the hydrogenation efficiency of heterogeneous catalytic systems. To address this limitation, we developed a TiO2 modification strategy involving the in-situ formation of reducible TiO2 on Al2O3, resulting in a Ni/TiO2-Al2O3 catalyst with enhanced hydrogen spillover efficiency. The modified catalyst exhibits significantly improved activity for the selective hydrogenation of quinoline under identical reaction conditions. Comprehensive characterization and experimental results demonstrate that TiO2 incorporation facilitates H2 activation and generates abundant hydrogen migration pathways, thereby increasing the concentration of active hydrogen species on the Al2O3 surface. DFT calculations further confirm that the hydrogen migration barrier at the TiO2-Al2O3 interface is lower than that of pure Al2O3, offering theoretical support for the enhanced spillover efficiency. Meanwhile, the spatial separation between quinoline adsorption sites, Lewis acid of Al2O3 and hydrogen activation sites, Ni nanoparticles, directly drive the enhanced hydrogenation performance. Furthermore, the use of an i-PrOH/ H2O mixed solvent significantly enhances catalysis, as water mediates the spillover of active hydrogen species from the catalyst into the aqueous phase, where they participate in the reaction via a Grotthuss proton-hopping mechanism, as evidenced by NMR. Delayed feeding experiments demonstrate that hydrogen stored in the aqueous phase can still drive quinoline hydrogenation even after H2 removal, highlighting the importance of both solid- and liquid-phase hydrogen transfer. This dual-phase spillover strategy offers a promising avenue for designing highly efficient heterogeneous catalytic hydrogenation systems.

The selective catalytic hydrogenation of furfural to 1,5-pentanediol (1,5-PeD) is a transformation of important scientific significance. This process proceeds through the initial hydrogenation of furfural to tetrahydrofurfuryl alcohol (THFA), followed by selective cleavage of the C-O bond at the C2 position mediated by active sites on the catalyst surface. However, precise control of C-O bond cleavage remains a major challenge, often resulting in undesired byproducts such as 1,2-pentanediol (1,2-PeD). Herein, a Co4/La2O3-CA-850 catalyst rich in oxygen vacancies (Ov) and LaH x species was synthesized via a citric acid (CA) sol-gel method. After high-temperature reduction with H2, a well-defined interfacial structure of Co-La2O3 emerged, and it played a critical role in the catalytic process. This interface effectively adsorbed oxygen atoms from THFA and enabled selective activation of the C2 site through hydrogen species (H-) derived from LaH x , facilitating highly efficient C2-O2 bond cleavage. Mechanistic study also clearly demonstrated the reaction pathway. Finally, the catalytic system realized a 64.9% yield of 1,5-PeD. These findings underscore the potential application of Co/La2O3-based catalysts for biomass upgrading and establish a sustainable, environmentally benign route for 1,5-PeD preparation.

The oxidative esterification of biomass-derived furfural is a sustainable pathway to value-added chemicals, yet current catalytic systems typically require harsh oxidants and alkali additives, which limit scalability and complicate downstream processing. Herein, a single-atom manganese catalyst (MnSA@CN) with atomically dispersed Mn-N4 sites is fabricated by coordinating Mn2+ with 1,4-diazabicyclo[2.2.2]octane (N(CH2CH2)3N, DABCO), followed by controlled thermal treatment and acid leaching. Under mild, additive-free conditions (90 °C, ambient-pressure air), MnSA@CN affords quantitative conversion of furfural to methyl furoate with >99% selectivity in a single step. Radical scavenging experiments combined with density functional theory calculations reveal a cooperative activation mechanism: the Mn-N4 sites synergistically activate O2 and furfural, generating methanol-derived hydroxyl radicals that mediate direct C-H oxidation and esterification, thereby bypassing the conventional furoic acid intermediate. This work highlights the pivotal role of isolated Mn-N4 centers in substrate-oxidant coactivation and delivers a scalable, noble-metal-free catalytic platform for sustainable biomass valorization, bridging fundamental single-atom catalysis with practical biorefinery transformations.

Lignin derivatives are considered a renewable resource and their efficient utilization and clean conversion have attracted increasing research attention. However, construction of efficient catalytic system for large-scale transformation of lignin derivatives to production value-added fine chemicals under mild reaction conditions remains a significant challenge. Herein, a Ga2O3-supported bimetallic catalyst was developed, by incorporating cobalt into Ga2O3 and depositing nickel onto its surface, the Co5Ni5/Ga2O3 catalyst was successfully constructed, which resulted in the formation of abundant oxygen vacancies and enabled hydrogen spillover on the non-reducible Ga2O3 support. This modification endowed Co5Ni5/Ga2O3 catalyst with hydrogenation capability and significantly enhanced its catalytic activity. The hydrodeoxygenation of guaiacol achieved a cyclohexanol yield of up to 95.1% under mild reaction condition of 180 degrees C, 1.2 MPa as compared with noble metal-based catalysts. Mechanism study confirmed that nickel facilitates homolytic hydrogen cleavage, while cobalt doping enhances guaiacol adsorption and the energy barrier for hydrogen transfer decreased from 0.52 to 0.24 eV, which confirm the efficient hydrodeoxygenation of guaiacol. This study provides a novel strategy for enhancing hydrogen spillover for catalyst design in the hydrodeoxygenation of guaiacol.

The semi-hydrogenation of alkynes plays a vital role in the petrochemical and fine chemical industries, however, achieving a balance between high activity and selectivity remains a significant challenge. In this study, mesoporous nitrogen-doped carbon spheres (NCS) enriched with pyridinic-N sites were synthesized through the in-situ pyrolysis of 3-aminophenol-based phenolic resin, enabling the immobilization of ultrafine PdCu nanoclusters. Experimental and theoretical results demonstrate that the alloyed Cu and pyridinic-N sites synergistically modulate the electronic structure and local microenvironment of Pd atoms in the PdCu nanoclusters. This coordination results in the weakest adsorption energy (-1.05 eV) for product alkenes and a d-band center of-1.48 eV, facilitating alkene desorption. Consequently, the optimized Pd1Cu1.5/NCS600 catalyst achieves 99.9% conversion and 98.1% selectivity for phenylacetylene semi-hydrogenation, with performance nearly unaffected by free styrene. The catalyst also exhibits long-term stability, a high turnover frequency (483.4 h-1), broad applicability, and gram-scale semi-hydrogenation with high selectivity and stability under mild conditions (30 degrees C, 1 atm H2). This work highlights that tailoring the chemical microenvironment of Pd active sites offers an effective strategy to simultaneously enhance catalytic activity and selectivity, offering promising potential for industrial applications in semi-hydrogenation processes.

The development of high-performance heterogeneous catalysts for the hydroformylation of olefins to produce aldehydes is significant. The incorporation of heteroatoms into polymeric or carbon nanospheres, aimed at improving catalytic activity and selectivity toward linear aldehydes has motivated extensive research efforts. Herein, we report the design of an N/P co-doped porous carbon nanomaterial derived from cyclotriphosphazene containing covalent organic framework (COF) for the immobilization of rhodium species. The resulting catalyst exhibited excellent performance in hydroformylation of styrene, achieving 99.9% conversion and 93.1% aldehyde selectivity, with a linear-to-branched (l/b) ratio of 1.71. Moreover, it demonstrated remarkable stability over 10 consecutive recycling tests, outperforming most reported Rh-based catalysts. Mechanistic studies reveal that the introduction of P significantly lowers the energy barrier along the linear aldehyde pathway, with the highest barrier reaching only 0.35 eV. This value was lower than that of branched aldehyde pathway under P-coordination (0.66 eV), indicating a reversal in regioselectivity favoring linear aldehydes. This work provides a generalizable strategy for the preparation of various metal-supported carbon-based catalysts with heteroatoms doping for catalytic applications.

Hydroformylation of olefins to produce high-value aldehydes is among the most important processes in the chemical industry. However, heterogeneous hydroformylation catalysts still face major challenges, including limited selectivity toward linear aldehydes, low catalytic activity, and poor stability. In this study, we developed a phosphorylation strategy to synthesize a hollow phosphorus- and nitrogen-codoped carbon material encapsulating Rh nanoclusters as a confined catalyst (Rh-CNP). The incorporation of phosphorus induces a significant electronic effect that enhances selectivity in alkene hydroformylation, achieving a linear-to-branched aldehyde ratio above 7. Mechanistic analysis shows that the formation pathway for linear aldehydes has a lower energy barrier, resulting in a selectivity of 87.8% in the hydroformylation of 1-octene. Furthermore, the spatial confinement structure significantly improves catalyst stability, maintaining consistent performance over ten reaction cycles. The one-pot synthesis of the Rh-CNP catalyst through in situ phosphorylation enables precise control of phosphorus content and offers new insights into the selective hydroformylation of alkenes as well as the design of highly stable confined catalytic systems.

The selective catalytic deoxygenation of oxy-organics in Fischer-Tropsch mixed oil for its high value utilization is challenging. Herein, a BaCO3/gamma-Al2O3 catalyst was prepared calcining gamma-Al2O3 with BaCO3, and the acid-alkalinity of the catalyst was regulated by introducing alkaline Ba basic sties. In a continuous fixed-bed reactor with a feed mass space velocity of 1 h(-1) and reaction temperature of 330 degrees C, BaCO3/gamma-Al2O3 catalyst can efficiently catalyzed the deoxygenation removal of 1-octanol in Fischer-Tropsch C10 mixture oil. It also inhibited the isomerization of 1-decene in the C10 mixture. The catalytic deoxygenation kinetics of 1-octanol were also studied. The reaction was endothermic with an activation energy of 64 kJ.mol(-1) and a reaction order of 2. In addition, theoretical studies revealed the adsorption and activation of 1-decene on the Lewis acidic site and the alkaline Ba basic sites, 1-decene was more easily underwent isomerization into 2-decene at Lewis acid sites. This research provides a useful method to enable the industrial application of catalytic deoxygenation of alcohols in Fischer-Tropsch synthetic oil. (c) 2025 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

The efficient catalytic conversion of the biomass platform molecule furfural into biofuels or other high-valueadded chemicals is currently a research hotspot. However, the hydrogenation of furfural possesses challenges due to the occurrence of multiple side reactions that generate various by-products. Herein, S-doped mesoporous carbon spheres (CS-S) with an ordered and accessible structure were precisely designed and synthesized. Subsequently, similar to 1.8 nm Pd nanoclusters were immobilized within the radial mesoporous structure of CS-S to obtain a Pd/CS-S catalyst. This catalyst was used for the hydrogenation of furfural and acetophenone into tetrahydrofurfuryl alcohol (THFA) and 1-phenylethanol, respectively, and 99 % conversion and more than 90 % selectivity were achieved. Mechanistic study revealed that the electron-deficient Pd nanoclusters anchored on CS-S exhibit higher adsorption energies for reactant molecules, thus facilitating the pre-adsorption and activation of substrate molecules. Moreover, the Gibbs free energy for each step of the hydrogenation process is lower on the electron-deficient Pd metal surface, leading to excellent catalytic hydrogenation performance. In addition, the Pd/CS-S catalyst also exhibited remarkable recyclability and stability over multiple reaction cycles. This work facilitates the construction of stable metal nanocluster-based catalysts for enabling highly selective catalytic hydrogenation.

Dual single-atom catalysts have attracted considerable research interest due to their higher metal atom loading and more flexible active sites compared to single-atom catalysts (SACs). We pioneered the one-step synthesis of sheets copper-cobalt graphitic carbon nitride dual single-atom (S-Cu/Co-g-C3N4) using folding fan-shaped aluminum foil as a template, and used them as catalysts in the epoxidation of styrene respectively. Through XAFS (X-ray Absorption Fine Structure) and other characterizations, it is found that Cu and Co single atoms are stabilized separately on g-C3N4 via coordination with nitrogen (N), hindered the ordered growth of sheets, and formed more pore structures, which not only increased more catalytically active sites, but also effectively prevented the flakes re-aggregate during the catalytic process. And the synergistic effect between Cu and Co changes the energy band structure of the material and facilitates electron transfer during catalysis, hence an excellent catalytic effect of 89 % styrene conversion and 85 % styrene oxide selectivity was achieved when S-Cu/Co-g-C3N4-1 : 1 was applied in the epoxidation of styrene. Furthermore, the mechanisms of the epoxidation of styrene with S-Cu/Co-g-C3N4-1 : 1 was probed by the density functional theory (DFT) based on the slab model.

The semi-hydrogenation of alkynols to produce high-value enols is a critical transformation in the fine chemicals industry, yet achieving high selectivity while avoiding over-hydrogenation remains a formidable challenge for Pd-based catalysts. Herein, we present the synthesis of Pd nanoclusters anchored on N-doped porous carbon spheres (Pd/N-PCS) through a co-self-assembly approach combined with a small-molecule-assisted strategy. The mesoporous Pd/N-PCS catalyst, featuring abundant pyridinic-N and pyrrolic-N species, precisely modulates the electronic properties of active Pd sites. Under mild conditions, Pd/N-PCS achieves exceptional performance with 99 % conversion and selectivity in alkynol semi-hydrogenation, outperforming most reported Pd-based catalysts. Mechanistic investigations demonstrate that N-site coordination fine-tunes the electronic states of Pd nanoclusters, resulting in weak adsorption of enol products and effectively suppressing their over-hydrogenation. Moreover, Pd/N-PCS exhibits remarkable versatility in the semi-hydrogenation of diverse alkynols and maintains robust catalytic activity across multiple cycles. This study not only advances the design of efficient metalnanocluster catalysts but also establishes a practical route for the selective synthesis of high-value enols, offering significant potential for industrial applications.

The controlled fabrication of metal nanocluster-based catalysts with high catalytic performance and stability is currently a research hotspot, while it is still a research challenge. Herein, nitrogen-doped mesoporous carbon spheres (CS-N) with a regular and open structure were precisely designed and prepared. Pd nanoclusters with an average size of 1.44 nm were highly dispersed and stably confined in the radial mesoporous structure of CS-N, forming Pd/CS-N catalysts. The obtained Pd/CS-N catalysts showed high catalytic performance in the hydrogenation of phenol to cyclohexanone and hydrogenation of benzoic acid to cyclohexanecarboxylic acid (yield of almost 99%) under mild reaction conditions, outperforming most reported Pd nanoparticle-based catalysts. Theoretical calculation illustrates that the Pd nanocluster exists as an electron-deficient state on Pd/CS-N, thus can efficiently facilitate reactant preadsorption and activation, and also reduce the Gibbs free energy of the rate-determining step of the hydrogenation reactions. Moreover, the Pd/CS-N catalyst exhibited good reusability and stability. Thus, this work will promote the precise construction of stable metal nanocluster-based catalysts, enabling highly efficient catalytic hydrogenation reactions.

The selective hydrogenation of alkynes to alkenes is widely applied in the chemical industry; nevertheless, achieving highly selective hydrogenation with high catalytic activity is considerably challenging. Herein, ultrafine PdCu bimetallic nanoparticles encapsulated by high-surface-area mesoporous α-Al2O3 were prepared by high-temperature calcination-reduction using a porous organic framework (POF) as the template. As-obtained PdCu@α-Al2O3 exhibited a high selectivity of 95% for the semi-hydrogenation of phenylacetylene as a probe reaction under mild reaction conditions. The separation of continuous Pd atoms and modification of the Pd electronic state by Cu atoms suppressed β-hydride formation and alkene adsorption, contributing to high selectivity for the catalytic hydrogenation of alkynes. The catalytic activity was maintained after 7 cycles due to the strong interaction between the PdCu bimetallic nanoparticles and α-Al2O3 as well as the encapsulation effect of mesoporous α-Al2O3. Thus, the current work provides a facile strategy for fabricating high-surface-area mesoporous α-Al2O3-supported catalysts for industrial catalysis applications.

The hydroformylation of alkenes to prepare aldehydes using rhodium-based catalysts has been widely investigated, while homogeneous Rh catalysts always suffer from poor reusability. Herein, a promising solution was proposed to introduce phosphorous heteroatoms into a porous carbon support to fabricate a stable and efficient catalyst (Rh/P-mC). And the obtained Rh/P-mC had high hydroformylation activity under mild reaction conditions. The substrate expansion experiment using different alkene substrates and the catalyst cycling experiment demonstrated the universality and stability of this catalyst. The hydroformylation reaction mechanism was also proposed, and the effect of the interaction between phosphorus and rhodium on the hydroformylation reaction was verified. Thus, this work has great application prospects for the highly efficient catalytic hydroformylation of alkenes and provides an efficient method for the design of high-performance hydroformylation catalysts.

Chemoselective hydrogenation of unsaturated organic compounds is a significant research topic in the catalysis field. Herein, a sulfur-doped ordered mesoporous carbon (SMC) material was prepared to anchor ultrafine platinum (Pt) clusters for the chemoselective hydrogenation of halogenated nitroarenes. The confinement effect of the ordered pores and the strong metal-support interaction caused by Pt clusters and sulfur atoms, efficiently suppress the aggregation and regulate the electronic states of the ultrafine Pt clusters. Thus, the hydrogenation of parachloronitrobenzene (p-CNB) shows high selectivity catalyzed by the ultrafine Pt clusters with electron-rich states. Meanwhile, the catalytic performance of the hydrogenation reaction catalyzed by Pt/SMC is capable of being maintained after at least 5 cycles, and the catalytic universality can also be applied to different halogenated nitroarenes hydrogenation. Therefore, this study may promote the research into the construction of noble metal-based catalysts for chemoselective hydrogenation reactions in green and sustainable chemical processes.

The catalytic transformation of the biomass platform compound levulinic acid (LA) to γ-valerolactone (GVL) is a vital reaction to produce related renewable chemicals and fuels. Developing stable catalysts with highly dispersed and accessible ultrafine metal nanoparticle (NP) active sites for the hydrogenation of LA under solvent-free conditions is still a major challenge. Herein, a versatile nano-emulsion self-assembly method was employed to fabricate N-doped carbon nanospheres with a high specific surface area and hierarchically porous structure. Ultrafine Ru NPs were successfully anchored on the hierarchal porous N-doped carbon nanospheres (HPNC) with high dispersion. The obtained Ru/HPNC catalyst exhibited excellent catalytic performance for LA hydrogenation to GVL under solvent-free conditions with outstanding reusability. In contrast, Ru NPs embedded in other supports (including activated carbon and carbon nanotubes) were observed to be less effective under the same reaction conditions. The superior catalytic performance of the Ru/HPNC catalyst is due to the hierarchically porous catalyst structure, and accessible ultrafine Ru active sites which can promote the activation of CO bonds and H2 absorption during the catalytic process. The reaction pathway of LA hydrogenation to GVL is clearly researched by theoretical calculations. Thus, the current work provides a facile strategy for the synthesis of highly dispersed ultrafine metal NP-based catalysts for an important biomass transformation.