Strong metal-support interaction (SMSI) is one of the most important concepts in heterogeneous catalysis. Triggered by pretreatment or reaction processes, the supported metal nanoparticles may be partially or completely encapsulated by support-derived overlayers, which impact the catalytic performance of supported metal catalysts. However, the formation mechanism of the SMSI state is still unclear.
　　Recently, a research team led by Prof. FU Qiang from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) proposed a gas-phase migration route for the formation of SMSI.
　　This work was published in Angewandte Chemie International Edition on Dec. 11.
　　Schematic illustration of the formation of self-limited Cu@ZnOx structure via gas-phase migration route and its effect on CO2 hydrogenation to methanol over Cu/Al2O3 catalysts (Image by SONG Tongyuan)
　　So far, two diffusion routes of the support-derived species onto the metal surface have been suggested, including interface alloying and surface migration.
　　In this work, the researchers placed ZnO particles and Cu/Al2O3 powders in a microreactor in a dual-bed mode (ZnO||Cu/Al2O3). By utilizing gas-phase migration of Zn species in CO2/H2 atmosphere (0.5% CO2/H2, 450°C), they found a self-limited thin ZnOx overlayer grew on the surface of Cu nanoparticles (Cu@ZnOx) in the Cu/Al2O3 catalyst without excessive deposition and aggregation of ZnOx species. Thus, they obtained an optimal number of ZnOx-Cu interface sites, which enhanced the methanol synthesis activity.
　　Moreover, the researchers demonstrated that the formation of the self-limited Cu@ZnOx encapsulation structure was due to the evaporation of Zn atoms from the ZnO particles, migration to the Cu/Al2O3 catalyst, and further deposition onto the Cu surface to form ZnOx overlayers under the synergistic effect of reducing H2 and oxidizing CO2 components at the treatment temperature.
　　"Our work elucidates the high temperature redox atmosphere-induced gas-phase migration route to the formation of the encapsulation structure or the classic SMSI state," said Prof. FU.
　　This work was supported by the National Key R&D Program of China, the National Natural Science Foundation of China, and the Photon Science Center for Carbon Neutrality.

　　Selective hydrogenation of carbon monoxide (CO) to higher alcohols (C2+OH) is a promising non-petroleum route for producing high-value chemicals, in which precise regulations of both C-O cleavage and C-C coupling are highly essential but remain challenges.
　　Recently, a research group led by Prof. DENG Dehui and Assoc. Prof. YU Liang from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS), in collaboration with Prof. WANG Ye from Xiamen University, realized highly selective CO hydrogenation to C2-4OH over a potassium-modified edge-rich molybdenum disulfide (ER-MoS2-K) catalyst.
　　This study was published in Nature Communications on Oct. 26.
　　Tunable CO hydrogenation selectivity over MoS2-based catalyst (Image by HU Jingting and WEI Zeyu)
　　The ER-MoS2-K catalyst, which was assembled in nano-array morphology with uniform linear channels, was prepared on the basis of a nano channel-confined growth mechanism.
　　The researchers found that it could deliver a high CO conversion of 17% with a superior C2-4OH selectivity of 45.2% in hydrogenated products at 240 oC and 50 bar. Moreover, by reducing the lateral size of MoS2 to enrich the edges for boosting the carbon-chain growth, the researcher achieved the C2-4OH to methanol selectivity ratio overturn from 0.4 to 2.2, and the selectivity of C2-4OH could reach to over 99% in the C2+OH products.
　　In-situ characterizations combined with theoretical calculations revealed that the sulfur vacancies (SVs) at the edge of MoS2 boosted carbon-chain growth by facilitating simultaneously the C-O cleavage of CHxO* for generating CHx* intermediate, and the subsequent C-C coupling between CO* and CHx*, while the potassium promoter promoted the desorption of alcohols via electrostatic interaction with hydroxyls, thereby enabling controllable formation of C2-4OH.
　　"This work presents the high flexibility of edge SVs of MoS2 in tailoring both C-O cleavage and C-C coupling for carbon-chain growth in CO hydrogenation, thus providing a prototype for the rational design of the nanostructure and microenvironment of active sites for selective hydrogenation reactions," said Prof. DENG.
　　This work was supported by the National Key R&D Program of China, the National Natural Science Foundation of China, the Strategic Priority Research Program of CAS, and the Fundamental Research Funds for the Central Universities.

　　Terpenoids are widely used in clinical therapeutics and medicinal discovery, as well as play important roles in cosmetic, food and perfume industries. In nature, terpenoids are synthesized from isopentenyl pyrophosphate and dimethylallyl pyrophosphate through multistep enzymes catalysis.
　　Since terpenoids are important, developing selective synthesis of terpenoids from bulk chemicals by mimicking the biological process is necessary.
　　Recently, a team led by Prof. CHEN Qing'an from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) developed a bioinspired and catalytic transformation of isoprene.
　　Their findings were published in Nature Communications on Nov. 04.
　　Isoprene is considered as cost-effective choice for biomimetic constructions of terpenoids due to its characteristic structure and abundance.
　　In terms of the synthesis of hemiterpenoids and acyclic monoterpenoids, various catalytic systems have been well developed under transition metal catalysis. However, there are many challenges, such as chemo-, regio- and redoxselectivities, to realize the nucleophilic cyclictelomerizations of isoprene, especially nucleophilic aromatization.
　　Nucleophilic aromatization of monoterpenes from isoprene (Image by ZHANG Weisong)
　　In this study, the researchers developed a new strategy to realize nucleophilic aromatization of monoterpenes from isoprene under nickel/iodine cascade catalysis, and it could be applied to various nucleophiles such as indoles, indazoles, benzotriazole and pyrroles.
　　In this strategy, a series of natural terpenes were transformed to aromatic C10 or C15 blocks by I2 catalysis. Based on the good tolerance of different monoterpenes, the convergent synthesis strategy was implemented smoothly by using drugs and plant extracts.
　　Meanwhile, the researchers also indicated the possible catalytic pathways of this strategy. Firstly, through the regulation of IPr ligand, the cyclodimerization of isoprene proceeded under Ni catalysis. Then, In the presence of K2S2O8, a highly selective nucleophilic addition occurred quickly following the oxidative aromatization of limonene under I2 catalysis.
　　Moreover, they realized the orthogonal C–H functionalization of two regioisomers of monoterpene with different nucleophiles in one same pot. And various hybrid terpenyl indoles were programmatically assembled to illustrate the practical utility of this protocol.
　　The above work was supported by Dalian Outstanding Young Scientific Talent and the National Natural Science Foundation of China.

　　Transition metal hydrides (TMHs) can be used as high-efficiency catalysts for hydrogen-involving reactions due to their finely modulable electronic states and reaction paths by interstitial hydrogen.
　　However, their severe thermodynamic instability brings challenges for preparation and utilization under ambient conditions.
　　Structural properties of surface ligand-confined 2D rhodium hydride (Image by FAN Jinchang)
　　Recently, a research group led by Prof. DENG Dehui and Assoc. Prof. YU Liang from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) constructed novel ambient-stable two-dimensional (2D) TMHs which are rhodium hydride (RhH) nanosheets.
　　This study was published in Matter on Sep. 28.
　　TMHs are usually thermodynamically unstable with positive formation free energies under standard conditions and thus can only be formed under immense H2 pressure (at least several GPa) or highly reductive conditions.
　　So far, palladium hydride is the only-reported ambient-stable TMH owing to its relatively strong interaction between Pd and H, while preparation and utilization of novel Pd-free ambient-stable TMHs under mild conditions is still unachieved.
　　In this study, the researchers used electron-attracting n-butylamino ligands to enhance the interaction between Rh and interstitial hydrogen, making the formation of 2D RhH thermodynamically permissible. It exhibited a superior hydrogen evolution reaction (HER) activity with a lower overpotential and 3.1 times and 1.4 times higher mass activity than 2D Rh catalyst and commercial Pt/C catalyst, respectively.
　　Moreover, the theoretical calculations revealed the significant effect of interstitial H atoms and surface ligands in boosting the HER activity of Rh, by moderately weakening hydrogen adsorption and accelerating H2 desorption via a ligand-mediated H-transfer mechanism
　　This work was supported by the National Natural Science Foundation of China, National Key R&D Program of China and the Young Cross Team Project of CAS.

　　The electrochemical CO2 reduction reaction (CO2RR) into carbon-based fuels provides a promising strategy to mitigate the CO2 emission and promotes the utilization of renewable energy.
　　The Cn (n≥2) liquid products are desirable because of their high energy densities and ease of storage. However, manipulation of C-C coupling pathway remains a challenge due to the limited mechanistic understanding.
　　Recently, a research group led by Profs. ZHANG Tao and HUANG Yanqiang from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has developed a Sn-based tandem electrocatalyst (SnS2@Sn1-O3G), which could reproducibly yield ethanol with a Faradaic efficiency of up to 82.5% at -0.9 VRHE and a geometric current density of 17.8 mA/cm2.
　　The study was published in Nature Energy on Oct. 30.
　　The researchers fabricated the SnS2@Sn1-O3G through solvothermal reaction of SnBr2 and thiourea on a three-dimensional carbon foam. The electrocatalyst comprised SnS2 nanosheets and atomically dispersed Sn atoms (Sn1-O3G).
　　Mechanistic study showed that this Sn1-O3G could respectively adsorb *CHO and *CO(OH) intermediates, therefore promoting C-C bond formation through an unprecedented formyl-bicarbonate coupling pathway.
　　Moreover, by using isotopically labelled reactants, the researchers traced the pathway of the C atoms in the final C2 product formed over the catalyst of Sn1-O3G. This analysis suggested that the methyl C in the product comes from formic acid whereas the methylene C was from CO2.
　　"Our study provides an alternative platform for C–C bond formation for ethanol synthesis and offers a strategy for manipulating CO2 reduction pathways towards desired products," said Prof. HUANG.
　　This work was supported by the National Natural Science Foundation of China and CAS Project for Young Scientists in Basic Research.

　　In the petrochemical industry, light linear/branched alkane isomers (C5-C7) need to be effectively separated for different end uses, linear alkanes are to be cracked for ethylene production, whereas branched isomers are to be used for gasoline upgrading.
　　Recently, a research group led by Prof. YANG Weishen and Prof. BAN Yujie from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) split linear alkanes from mono-branched and di-branched isomers as well as their cyclical counterparts through oriented metal-organic framework (MOF) membrane.
　　This study was published in Nature Communications on Oct. 19.
　　MOFs bring tremendous opportunities for membrane separation. HKUST-1 is an archetypal MOF with a combination of di-nuclear copper paddlewheel units and 1,3,5-benzenetricarboxylic acid to form a face-centered cubic network.
　　In this study, the researchers indicated that {111}-oriented HKUST-1 membranes were capable of splitting linear alkanes from branched isomers (or cyclical counterparts) by virtue of the size repulsion mechanism, since the rigid triangular pore with a size of ~0.46 nm running through {111} crystal facets was positioned between the kinetic diameters of alkane isomers.
　　The anisotropy of the porous HKUST-1 architecture and C5-C7 alkane isomer separation through {111}-oriented HKUST-1 membranes at 30°C (Image by BAN Yujie and WANG Yuecheng）
　　In this study, the {111}-oriented HKUST-1 membranes were formulated according to the morphology-biased principle and finally realized with a low dose synthesis method for terminating undesired crystal nucleation and growth. This membrane could realize one-step extraction of normal-pentane, normal-hexane and normal-heptane from a ten-component alkane isomer solution that mimicked light naphtha.
　　This work was supported by the National Natural Science Foundation of China and the Youth Innovation Promotion Association of CAS.