摘要：The reaction mechanism of zeolite- or zeotype-catalyzed methanol-to-olefins（MTO） conversion is still a subject of debate. Employing periodic density functional theory calculations, the olefin-based cycle was studied using tetramethylethene（TME） as a representative olefinic hydrocarbon pool in H-SAPO-18 zeotype. The overall free energy barrier at 673 K was calculated and found to be less than 150 kJ/mol in the TME-based cycle, much lower than those in the aromatic-based cycle（〉 200 kJ/mol）, indicating that olefins themselves are the dominant active hydrocarbon pool species in H-SAPO-18. The similarity of the intermediates involved between the aromatic-based cycle and the olefin-based cycle was also highlighted, revealing that both cycles were pattern-consistent. The selectivity related to the distribution of cracking precursors, such as higher olefins or carbenium ions, as a result of the olefin-based cycle for the MTO conversion. The enthalpy barrier of the crack-ing step scaled linearly with the number of carbon atoms of cracking precursors to produce ethene or propene with ethene being much less favored than propene for cracking of C7 and higher pre-cursors. This work highlighted the importance of the olefin-based cycle in H-SAPO-18 for the MTO conversion and established the similarity between the olefin-based and aromatic-based cycles.

摘要：Electrocatalytic ammonia synthesis under mild conditions is an attractive and challenging process in the earth’s nitrogen cycle,which requires efficient and stable catalysts to reduce the *** N2 activation and reduction overpotential of different Ti3C2O2-supported transition metal(TM)(Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Mo,Ru,Rh,Pd,Ag,Cd,and Au)single-atom catalysts have been analyzed in terms of the Gibbs free energies calculated using the density functional theory(DFT).The end-on N2 adsorption was more energetically favorable,and the negative free energies represented good N2 activation performance,especially in the presence Fe/Ti3C2O2(﹣0.75 eV).The overpotentials of Fe/Ti3C2O2,Co/Ti3C2O2,Ru/Ti3C2O2,and Rh/Ti3C2O2 were 0.92,0.89,1.16,and 0.84 eV,*** potential required for ammonia synthesis was different for different TMs and ranged from 0.68 to 2.33 *** possible potential-limiting steps may be involved in the process:(i)hydrogenation of N2 to*NNH and(ii)hydrogenation of*NH2 to *** catalysts can change the reaction pathway and avoid the traditional N–N bond-breaking *** also simplifies the understanding of the relationship between the Gibbs free energy and overpotential,which is a significant factor in the rational designing and large-scale screening of catalysts for the electrocatalytic ammonia synthesis.

摘要：The selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines(py-THQ) and its derivatives has attracted a considerable amount of attention as they show great versatility in many pharmaceuticals, agrochemicals, and fine chemicals. Over the past few decades, great breakthroughs have been achieved in the controlled synthesis of efficient heterogeneous catalysts used for the selective hydrogenation of functionalized quinoline compounds, which allow one to correlate the structure-property relationships. In this review, we will summarize the recent significant progress achieved in this field covering the synthetic strategies, microstructural and chemical features, catalytic performance, and internal relationships. state-of-the-art noble metal-based single(Pd, Pt, Ru, Rh, Ir and Au) and bi/multi-metallic catalysts(RuCu, AuPd, and PdNi) are first introduced, followed by a summary of earth-abundant metal-based catalysts(Co, Fe, Ni, and Cu). Finally, the dehydrogenation of N-heterocycles is introduced to form a reversible hydrogenation/dehydrogenation system for H2 storage, which can be employed in a liquid organic hydrogen system. Furthermore, the reaction mechanism and future research direction in these areas are also discussed. This review will deepen our understanding of the catalytic transformation of N-heterocycles and provide guidance for researchers on the rational design of catalysts.

摘要：The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes,especially eco-friendly and intrinsically safe *** idea is to improve the selectivity,activity,and stability of the catalyst in an appropriate ***,it is of great academic and industrial significance to conduct in-situ characterization of a working catalyst while testing its catalytic *** is beneficial for a comprehensive study on the dynamic evolution of the catalyst structure under real conditions,deepening the understanding of the structure-performance relationship of catalysts,and providing a scientific basis for the development of future generation catalytic *** far,it is still a great challenge to realize full life cycle characterization of heterogeneous catalysts from catalyst formation and function to deactivation under real world *** this mini review,we summarize the characterization strategies for heterogeneous catalysts,using zeolite,metal,and metal oxide catalysts as typical *** research strategies for the approximation of industrial conditions,multi-scale in-situ characterization devices,and computational modeling of realistic conditions should provide insight for the research and development of industrial catalysis.

摘要：Obtaining a detailed understanding of the surface modification of supports is crucial;however,it is a challenging task for the development and large-scale fabrication of supported electrocatalysts that can be used as alternatives to Pt-based catalysts for the oxygen reduction reaction(ORR).In this study,commercial silicon carbide(SiC)was modified through surface oxidization(O-SiC)to support the use of Pd nanoparticles(Pd NPs)as electrocatalysts for *** obtained Pd/O-SiC catalysts exhibited better ORR activity,stronger durability,and higher resistance to methanol poisoning than that exhibited by commercial Pt/*** role of the support in enhancing the ORR performance,especially the oxidization of SiC surfaces,was discussed in detail based on the experimental characterizations and density functional theory *** underlying mechanism of the superior ORR performance of Pd/O-SiC catalysts was attributed to the charge transfer from SiC_(x)O_(y)to Pd NPs on the surfaces of SiC and the strong metal–support interactions(SMSIs)between Pd and SiC_(x)O_(y).The charge transfer enhanced the ORR activity by inducing electron-rich Pd,increased the adsorption of the key intermediate OOH,and decreased the Gibbs free energy of the critical ORR ***,SMSIs enhanced the ORR stability of the Pd/O-SiC *** study provided a facile route for designing and developing highly active Pd-based ORR electrocatalysts.

摘要：The nitrogen reduction reaction(NRR)using new and efficient electrocatalysts is a promising al‐ternative to the traditional Haber‐Bosch ***,it remains a challenge to design efficient catalysts with improved catalytic ***,various O‐functional MXenes were investigated as NRR catalysts by a combination of density functional theory calculations and least absolute shrinkage and selection operator(LASSO)***_(3)C_(2)O_(X) has been regarded as a promising catalyst for the NRR because of its stability,activity,and *** poten‐tial‐determining step is*NH_(2) hydrogenation to*NH3 with a limiting potential of-0.45 ***‐more,via LASSO regression,the descriptors and equations fitting the relationship between the properties of O‐functional MXenes and NRR activity have been *** work not only pro‐vides a rational design strategy for catalysts but also provides machine learning data for further investigation.

摘要：Due to their tunable acidity,shape selectivity,and excellent stability,zeolites are of great importance as solid acid materials in industrial *** the properties of the acid sites in zeolites allows for the rational design and fabrication of catalysts for target *** ether(DME)carbonylation,a critical chain-growth reaction for C1 resource utilization,is selectively catalyzed by the Brønsted acid sites within the eight-membered rings(8-MRs)of mordenite(MOR).It is anticipated that strengthening the Brønsted acidity—particularly in 8-MRs—will improve the catalytic performance of *** this work,density functional theory(DFT)calculations are first employed and the results used to design a modified MOR with stannum(Sn)and to predict the corresponding changes in *** by the theoretical studies,a series of Sn-modified MOR are synthesized via a defect-engineering and subsequent heteroatom-substitution *** partial desilication,isolated tetrahedral Sn species in an open configuration are successfully synthesized for the first time,within which tetrahedrally coordinated Al sites are *** acidic characterization is used to confirm that the acidity of the Brønsted acid sites is enhanced by the introduction of the Sn species;as a result,the sample exhibits excellent activity in DME carbonylation *** and DFT studies reveal that this strengthened acidity facilitates the adsorption of DME and reduces the activation barriers of DME dissociation and acetyl formation,accounting for the improved *** work demonstrates mechanistic insights into the promoting effects of strong acidity on DME carbonylation and offers a promising strategy to precisely control the acidic strength of zeolites.