Cyclohexanones, as critical precursors for polyamide 6, are inherently challenging to synthesize from lignin-derived phenolic bio-oils due to the high dissociation energy of the aryl-OCH3 bond and the competitive risk of C=O bond over-hydrogenation. To address this intrinsic selectivity trade-off, we report the selective synthesis of cyclohexanones from lignin-derived phenolic monomers via a H2-free photothermal catalytic process using a RuPd/TiO2 photocatalyst at 150 °C, with a selectivity of 94% and an activity of 12 mol-one∙molRu+Pd-1∙h-1. Through the proton-coupled electron transfer process, photogenerated electrons drive precise aryl-OCH3 cleavage, and the resulting methoxy groups and water are utilized as internal hydrogen source. The low pressure of H* generated in situ is key to maintaining the high selectivity. The alkyl-substituted ketone is subsequently converted into the corresponding caprolactam monomer and copolymerized with conventional caprolactam. The propyl-functionalized polyamide 6 exhibits enhanced properties, including 88.9% transparency and 523% elongation at break, whereas conventional polyamide 6 (no alkyl) has only 71.5% transparency and 120% elongation, respectively. This work not only establishes a robust and chemically precise photothermal platform for selectively converting lignin to cyclohexanones, but also demonstrates that alkyl functionalization unlocks unprecedented properties in polyamide 6, thereby greatly increasing its value.

The deactivation of metal catalysts caused by sulfur poisoning has long been a major challenge in catalytic processes. Clarifying the response relationship between catalyst structure and sulfur poisoning is a crucial prerequisite for solving this problem. However, during preparation, the complex phase transitions between metals and carbon-based supports lead to the coexistence of multiple types of metal active sites, which trigger synergistic and competitive effects on the surface. This results in unclear sulfur resistance mechanisms and hinders the optimization of catalysts. In this study, through simple pyrolysis of precursors and identification of active site structures, three samples with different catalytic active site structures were obtained: exposed metal/oxide particles (Ni-NPs/C), nitrogen-doped metal-carbon aggregates (Ni-N-C), and graphitic carbon-coated metal/ oxide particles (Ni@C). Among them, the catalyst with Ni@C (OCPs-600-treated) can withstand the poisoning of various sulfur-containing substances (thiophene, thiourea, potassium thiocyanate) and shows excellent performance in 11 anti-sulfur cycles. Further deactivation and regeneration experiments indicate that it is not affected by sulfur electronic poisoning. In addition, combined with DFT and MD simulations, the key role of carbon layer encapsulation in suppressing the adsorption of sulfur species and ensuring the regeneration ability of the catalyst has been revealed.

Photothermal CO2 methanation offers a route to store renewable energy as synthetic methane, yet conventional Ni catalysts typically require intense light or auxiliary heating and show poor tolerance to intermittency. Here, we report a CeZrOx/NiO-Ni inverse catalyst via a heterostructure engineering strategy, featuring a protective NiO interlayer. This tailored architecture achieves 83% single-pass CO2 conversion with >99% CH4 selectivity under 0.71 W cm-2 irradiation in a continuous-flow system, without external heating. Notably, it delivers a CH4 space-time yield of 464 mmol·gcat -1·h-1 under natural concentrated sunlight and maintains robust performance over repeated light-dark cycles, extended air storage, and 100-g scaled synthesis, demonstrating its potential compatibility with intermittent renewable energy. Mechanistic studies reveal that the sub-nanometer NiO layer on Ni domains enhances LSPR-induced heating and hot-carrier injection while establishing a favorable CeZrOx/NiO-Ni band alignment for charge separation. This heterointerface further promotes CO2 activation via *COOH intermediates and electron-mediated pathways, thereby amplifying photothermal synergy under low-intensity illumination. This work highlights the critical role of interfacial engineering in advancing solar-driven energy conversion and provides a catalyst-level design strategy that could help bridge lab-scale innovation and future practical applications.

TS-1 zeolite is a catalyst known for its high selective oxidation performance and broad industrial applications. The titanium atom in the TS-1 often acts as the active center in catalytic reactions, especially in oxidation reactions, so increasing the titanium content in TS-1 is of great significance in chemical reactions and catalytic applications. This paper explores a Novel Boron Extraction and Titanium Incorporation Strategy to enhance the titanium content within the TS-1 framework. During the dry gel preparation process, boron species were introduced in situ into the framework of the TS-1 to form a framework boron-titanium-silicon TS-1-B with tetracoordinated or tri-coordinated positions. TS-1-B is then treated with acid to remove the framework boron, while an appropriate amount of titanium precursor is introduced to fill the vacancy left by the removal of the framework boron. The results of XRD, FT-IR, UV-Vis, BET, NH3-TPD, XRF, and XPS showed that the titanium content of the tetracoordinate framework in the TS-1 was improved. The catalytic performances of TS-1-B, TS-1BS, and TS-1-BST were comparatively evaluated through two representative reactions: propylene epoxidation and the direct synthesis of hydrogen peroxide from H2 and O2.

The presence of sulfur-containing impurities in industrial feedstocks leads to the rapid deactivation of metal-based catalysts, which originates from the specific recognition between the d orbitals of metallic active sites and the p orbitals of sulfur. In this work, a carbon-encapsulation catalyst strategy was employed to shield this specific d–p orbital recognition effect. The Pt-base catalyst showed a sharp 92.28% loss in activity after sulfur poisoning, whereas the carbon-encapsulated catalyst maintained high efficiency and stability, sustaining a reaction rate of 83.41 min–1 even at high mercaptan concentrations (7945 ppm). Moreover, it exhibited excellent reusability with negligible deactivation after five cycles. Characterization and density functional theory (DFT) calculations revealed that the carbon shell serves as “armor” for Pt active sites, physically isolating them from sulfur impurities and suppressing the hybridization between Pt nanoparticles (Pt NPs) and the S 2p orbitals. Meanwhile, Pt nanoparticles induce electron transfer to the carbon layer, converting it into a conductive “metallic carbon” that enhances hydrogenation activity. This work provides new insights into the anti-sulfur poisoning mechanism of catalytic hydrogenation.

The catalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid is a key step in the production of bio-based plastics but remains limited by sluggish multi-electron transfer kinetics across multiple reaction intermediates. In this study, we address this long-standing challenge by introducing a Mn-O-Co electron bridge within spinel CoMn2O4 to mediate and accelerate electron transfer. Through precise valence state regulation, we engineer a heterogeneous electron bridge dominated by Mn4+-O2--Co3+ linkages, enabling more efficient electron flow. Experimental characterization and theoretical calculations reveal that the incorporation of Mn4+ significantly enhances electron delocalization across the bridge. The empty eg orbitals of Mn4+ (t2g3eg0) serve as efficient electron acceptors, creating an energy-level gradient with Co3+ (t2g4eg2) that favors directional electron transfer. Simultaneously, Mn4+ strengthens metal-oxygen covalency, further improving electron mobility. This engineered electron bridge structure enables highly efficient cooperation across the full six-electron transfer pathway in 5-hydroxymethylfurfural oxidation, driven by a dynamic electron compensation mechanism. As a result, an 2,5-furandicarboxylic acid yield of 98.1% is achieved. This work offers a valuable theoretical foundation for understanding cooperative electron transfer in heterogeneous catalysis and provides a rational strategy for designing efficient electron bridge structures.

Boron nitride (BN) has a two-dimensional covalent structure and offers a catalytic platform for highly selective oxidative dehydrogenation of propane (ODHP). However, the limited structural tunability of pristine BN restricts its activity and stability under harsh conditions. Here, we demonstrate that highly curved BN surfaces in small-diameter multiwalled BN nanotubes promote ODHP activity via B-O sites at nitrogen vacancies, achieving over 20% propane conversion at 520 degrees C. These nanotubes are synthesized via a metal-free millisecond carbon thermal shock method, avoiding oxidative degradation. The resulting catalyst withstands temperatures up to 600 degrees C, and the local B-O/H environment impedes oxygen and water intrusion, ensuring stability over 100 h through multiple reaction cycles.

Carbon-encapsulated metal catalysts can have a high stability. The catalytic activation mechanism of the inert carbon shell requires further investigation. We prepared platinum-core carbon-shell catalysts on activated carbon supports. The graphitization degree of the carbon layer was tuned through pyrolysis temperature control. The catalysts were tested in the selective hydrogenation of p-chloronitrobenzene. The intact carbon shell physically isolates the metal core. All coated samples achieved a target product selectivity above 99%. The catalytic activity exhibited a distinct volcano trend. The sample treated at 800 °C delivered the highest activity. Experimental and theoretical analyses revealed an interfacial electron transfer process. The metal core acts as an electron pump to enrich the carbon surface. The optimal activity originates from a balance between electronic and geometric effects. The electron-rich surface lowers the hydrogen dissociation barrier. The preserved carbon defects serve as necessary adsorption sites. The core-shell structure suppressed metal sintering and the catalyst maintained good stability over 10 reaction cycles. This study provides a basic understanding for the design of highly active carbon-functionalized interfaces.

Nitrogen doping modulates the geometric and electronic structures of the carbon layer, thereby enabling the efficient hydrogenation–rearrangement of nitrobenzene to p -aminophenol.

Abstract The breakthrough in the performance of carbon-supported non-noble-metal catalysts lies in the synergistic optimization of geometric size and electronic structure; however, the high surface energy of metals tends to induce agglomeration, and the weak interfacial electronic coupling between metals and carbon makes precise regulation of electronic structure challenging. Herein, an incomplete encapsulation of Ni nanoparticles (Ni NPs) -embedded structure is achieved after the self-assembly of Ni species and halogen-doped carbon dots and the subsequent pyrolysis process. The F atoms, endowed with the strong electron-withdrawing capability, abstract electrons from the outer shell of Ni species, which not only accelerates interfacial electron transfer of the catalyst, thus modulating the d-band center of Ni, but also suppresses the formation of Ni−Ni bonds, thereby weakening the intrinsic driving force for metal agglomeration. Among them, the catalyst Ni@FCDs doped with F atoms exhibits the highest adsorption and dissociation ability for reactant molecules, demonstrated by the extended X-ray absorption fine-structure and density functional theory calculations, and the smallest metal particle size (5.54 nm), thus expressing high catalytic hydrogenation activity. Furthermore, the embedded structure effectively inhibits the sintering of Ni NPs during the reaction, and the metal particle size remains stable after 9 cycles of reaction. The synergistic optimization of geometric size and electronic structure of the metal species induced by the “halogen doping dual regulation” strategy provides an innovative approach for the design of high-performance nickel-based catalysts and deepens the understanding of the structure−activity relationship in carbon-supported metal catalysts.

Selective hydrogenation of trace acetylene in ethylene-rich streams is essential for polymer-grade ethylene. We prepared Pd-Cn/BN catalysts (n = 2, 4, 6, 8, 10) via a simple impregnation-reduction method using imidazolium chlorides with varied alkyl chains as modifiers. Molecular dynamics simulations reveal that H-2 diffuses about three orders of magnitude faster than C2H2 and C2H4 in [Cnmim][Cl], allowing preferential access of H2 to palladium (Pd) sites. Longer alkyl chains reduce overall gas diffusion but enlarge the C2H4-C2H2 diffusion difference, helping suppress over-hydrogenation. Catalytic tests identify Pd-C6/BN as the most active and selective catalyst; optimized 0.1Pd-30C6/BN delivers 99% C2H2 conversion and 90% C2H4 selectivity at 170 degrees C with stable performance over 120 h. Characterization and density functional theory show that [C6mim]Cl remains structurally intact, preferentially interacts with Pd, suppresses beta-PdHX formation, tunes Pd electronic structure and adsorption, and facilitates Pd reduction, underpinning the excellent catalytic performance.

A pyrrolic N-doped carbon encapsulated Pt/C catalyst was developed, through pyrolysis of in-situ polymerized polypyrrole overlayer on the Pt/C catalyst, for sulfur-resistant selective hydrogenation of halogenated nitroarenes. Such a core-shell structured catalyst with defective N-doped carbon layers not only blocked large sulfur compounds such as thiophene from accessing Pt sites, but also weakened the adsorption of small sulfur molecules like methyl mercaptan due to the decreased d-band owing to the pyrrolic N-doping. As a result, the catalyst exhibited high activity and outstanding sulfur tolerance in the hydrogenation of o-chloronitrobenzene, achieving >99% conversion and an o-chloroaniline yield of 40 g(o-CAN)g(Cat.)(-1)h(-1). It also maintained excellent stability over ten consecutive cycles in the presence of 600 ppm thiophene. Additionally, the PtN coordination between the Pt core and the pyrrolic N species at the carbon defects promoted electron transfer from Pt to the carbon layer. This electronic interaction enhanced the adsorption capacity for both reactants and H-2, while increasing the dechlorination energy barrier from 0.122 eV (over uncoated Pt) to 0.883 eV. Therefore, the selectivity toward dehalogenation can be suppressed below 3% for the selective hydrogenation of various halogenated nitroarenes.

Three new triterpenoids, henridilactones P-R (1-3) and two new dibenzocyclooctadiene lignans, henrilignans A and B (11 and 12), alongside twelve known analogues (4-10 and 13-17) were isolated from the stems and leaves of Schisandra henryi subsp. yunnanensis. The structures and absolute configurations of new compounds were elucidated by comprehensive 1D and 2D NMR, HRESIMS, electronic circular dichroism analyses, and theoretical calculations. In bioactivity evaluation, the isolated triterpenoids (1-10) exhibited moderate neurite outgrowth in differentiated PC12 cells at 10 µM (differentiation rates 10.09%-12.96%; positive control 50 ng/mL NGF, 19.71%). Furthermore, henridilactone P (1) exhibited a binding affinity with an equilibrium dissociation constant (KD) of 3.286 × 10- 4 M (reference compound PF-06446846, KD = 8.008 × 10- 5 M).

Carbon-encapsulated metal nanoparticles have found widespread applications in diverse chemical transformations, such as oxidation, hydrogenation, and reforming reactions. Herein, we report a facile and efficient strategy to construct ultrafine Pt nanoparticles encapsulated in N-doped defective graphene, which exhibit core-shell architectures, via in situ pyrolysis. The Pt/C@Nd12C700 catalyst with a predominant proportion of pyridinic N (49.02%) demonstrates significantly enhanced hydrogenation activity compared to Pt/C@Nr12C700. The combination of multiple characterization techniques and density functional theory (DFT) calculations further unveils that the optimized electronic structure and high dispersion of Pt arise from synergistic electronic and geometric effects. The pyridinic N triggers charge delocalization across the Pt-C interface and prompts charge redistribution among Pt, pyridinic N, and defective C sites, which induces distinct catalytic behavior on the traditionally inert external surface. The enhanced electronic interactions reconstruct the surface microenvironment of the catalyst, thereby rendering the carbon layer surface electron-abundant. Accordingly, the optimized adsorption energy of phenylhydroxylamine and the reduced activation barrier for H2 dissociation endow the pivotal phenylhydroxylamine intermediate with high specificity, enabling a relay coupling of catalytic hydrogenation and subsequent Bamberger rearrangement for the efficient production of p-aminophenol. This study presents a method for engineering the surface catalytic behavior of nitrogen-modified graphene-like confined Pt nanomaterials.

The development of efficient non-noble metal catalysts for selective hydrogenation of furfural to furfuryl alcohol is of great significance for the high-value conversion of biomass. However, precise regulation of the catalytic microenvironment to synergistically enhance reaction activity and selectivity remains challenging. This study used precipitation hydrothermal method to construct cobalt doped ceria supported iron catalyst and applied it to the efficient catalytic transfer hydrogenation of furfural. The optimized catalyst exhibited excellent catalytic performance and structural stability: a conversion of 99.33% for furfural and a selectivity of 99.50% for furfuryl alcohol could be achieved within 4 h, and there was no significant decrease in activity after 9 cycles of testing. In situ FT-IR spectroscopy and density functional theory calculations revealed that its superiority originated from the deep synergy between bimetallic and localized defects. Specifically, the introduction of iron species significantly enhanced the catalyst's ability to dissociate and activate hydrogen donors; cobalt doping not only promoted the enrichment of moderate basic sites by inducing the formation of oxygen vacancies, but also triggered the downward shift of the average d-band center, promoting substrate adsorption. The cobalt site adjacent to oxygen vacancies (Ov-Co) served as the optimal adsorption center, promoting the formation of the optimal adsorption configuration for furfural. Moreover, the appropriate proportion of iron-cobalt species constructed high concentrations of moderate Lewis acidic sites on the catalyst surface, driving the system to follow a highly selective MPV hydrogen transfer pathway. This work system elucidates the intrinsic mechanism of defect engineering and Lewis acid-base site synergistic enhancement of transfer hydrogenation, providing a novel strategy for the rational design of efficient and stable biomass conversion catalysts.

Developing catalysts for the cycloaddition reaction between carbon dioxide and epoxides under mild conditions is an important approach to achieve carbon dioxide fixation. In this study, we utilized NH3-ethanol solution at room temperature to promote the self-assembly of ionic liquids into a triazine structure, thereby avoiding environmental issues such as acid pollution associated with traditional methods. In addition, by controlling the amount of vinylbenzene used, the pore size distribution of hyper poly(ionic liquid)s (HPILs) can be concentrated (13.38 nm). It is worth noting that the catalyst exhibits excellent catalytic performance with a TOF as high as 185.7 h-1. It is 2-3 times greater than in previous studies. Through a series of characterization techniques, including X-ray photoelectron spectroscopy (XPS) and nitrogen adsorption-desorption isotherms (BET), it was proven that the catalyst constructed uniformly distributed synergistic catalytic sites (ILs-triazine). The triazine structure activates CO2 by bending its bond angle through pi-conjugation interactions, while the Lewis basic sites in ILs polarize the C-O bond to form alkyl halides. These two effects work synergistically to catalyze the cycloaddition reaction. Density functional theory (DFT) calculations clarified the reaction mechanism, laying the foundation for the development of metal-free multi-phase ring addition reaction catalysts.

Biochar-based catalysts show significant potential to replace toxic mercuric chloride in acetylene hydrochlorination. However, the mechanistic role of their non-metallic active sites remains scarcely investigated, particularly regarding the synergistic interplay between pore architecture and surface functionalities. Herein, a series of biochar based catalysts with rich microstructures were successfully prepared by using molten salt as medium, which were used in acetylene hydrochlorination. The method of preparing biochar by liquid medium of molten salt was optimized by adjusting the ratio of terpolymer salts, mesh number, constant temperature duration, reaction temperature and heating rate, etc. The materials were analyzed by BET, XRD, TGA, SEM and TEM. The results showed that the biochar materials had abundant pore structure and adjustable pore volume, and it was found that biochar with larger pore volume showed higher acetylene hydrochlorination conversion at the same pore size of 1.8 nm. Analysis suggests that biochar with large pore volume has more carbon "chambers" at the micropore size, which effectively promotes the "one-to-one" pairing of C2H2 and HCl molecules. This work found that the catalytic performance of acetylene hydrochlorination could be improved effectively by microstructural regulation of nonmetallic catalysts.

Strong metal-support interaction (SMSI) is typically observed between noble metals and reducible oxides. However, the precise control of SMSI over non-oxide supports and the realization of atomic-level interfacial engineering remain frontier challenges. Herein, we report a carboxyl-mediated SMSI strategy leveraging carboxyl-functionalized covalent triazine framework (CTFs) as structural templates to fabricate Pd nanoparticles encapsulated in tunable nitrogen-doped carbon shells. This tailored interfacial interaction enables deterministic regulation of the graphitic overlayer thickness, which evolves from a monolayer to a trilayer with modulated thermal treatment. Comprehensive characterizations, including suppressed surface adsorption, localized lattice contraction, and significant electron transfer from the metallic core to the carbon shell, verify the manifestation of SMSI effect. Computational simulations reveal that the initial encapsulation is thermodynamically spontaneous, while further shell growth requires higher thermal energy to overcome thermodynamic and kinetic barriers. This work extends the SMSI concept to precisely engineered CTF-derived carbon supports and establishes a reliable paradigm for the rational design of atomically precise, tunable catalyst interfaces, providing new strategies for developing high-performance catalysts beyond conventional systems.

Four new dichapetalin hybrid triterpenoids, namely phyllanfranchins A-D (1-4), were obtained from the aerial part of Phyllanthus franchetianus H. L'ev. (Phyllanthaceae), by ultra-performance liquid chromatography-quadrupole-time-of-flight tandem mass spectrometry (UPLC-Q-TOF-MS/MS) guided isolation strategy. The linkage of the phenethyl fragment with dammarane C-3 and C-29, along with esterification at C-25 by 4-hydroxyphenylpropanoic acid are unique in this unusual class of natural products. Their structures were elucidated by spectroscopic analysis, NMR calculations and DP4+ probability analyses, computational electronic circular dichroism (ECD) methods, and X-ray crystallography. Notably, compounds 1-2 and 4 exhibited potential cytotoxicity against six human cancer (HL-60, K562, A549, HepG2, MDA-MB-231, SW480) (IC50 = 3.38-40 μM) and one normal BEAS-2B (IC50 = 25.3-40 μM) cell lines. Among them, compound 1 exhibited potent activity against all six tumor cell lines tested (IC₅₀ = 3.38-5.21 μM), while demonstrating low cytotoxicity towards normal cells (> 40 μM). Mechanistic studies revealed that compound 1 induces apoptosis in A549 cells by altering the mitochondrial membrane potential via the Bcl-2/Bax signaling pathway.

Co–Ni alloy nanoparticles encapsulated in carbon are prepared via pyrolysis of metal–organic coordination polymer. The optimized catalyst delivers outstanding output performance in hydroxide exchange membrane fuel cells.