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Metal confinement catalyst MoS2/Pt@TD-6%Ti (TD, TS-1/Dendritic mesoporous silica nanoparticles composite) in dendritic hierarchical pore structures was synthesized and showed excellent sulfur-resistance performance and stabilities in catalytic hydrodesulfurization reactions of probe sulfide molecules. The MoS2/Pt@TD-6%Ti catalyst combines the concepts of Pt-confinement effect and hydrogen spillover of Pt noble metal. The modified micropores of Mo/Pt@TD-6%Ti only allow the migration and dissociation of small H2 molecules (0.289 nm), and effectively keep the sulfur-containing compounds (e.g. H2S, 0.362 nm) outside. Thus, the MoS2/Pt@TD-6%Ti catalyst exhibits higher DBT and 4,6-DMDBT HDS activities because of the synergistic effect of the strong H2 dissociation ability of Pt and desulfurization ability of MoS2 with a lower catalyst cost. This new concept combining H2 dissociation performance of noble metal catalyst with the desulfurization ability of transition metal sulfide MoS2 can protect the noble metal catalyst avoiding deactivation and poison, and finally guarantee the higher activities for DBT and 4,6-DMDBT HDS.

A dendritic PdCu/Ce0.3Zr0.7O2 (PdCu/CZ-3) catalyst with uniform spherical morphology was prepared for boosting the catalytic performance of CO2 hydrogenation to methanol (MeOH). The open dendritic pore channels and small particle sizes could reduce not only the diffuse resistance of reactants and products but also increase the accessibility between the active sites (PdCu and oxygen vacancy) and the reactants (H2 and CO2). More spillover hydrogen could be generated due to the highly dispersed PdCu active metals over the PdCu/CZ-3 catalyst. PdCu/CZ-3 can stimulate the generation of more Ce3+ cations, which is beneficial to produce more oxygen vacancies on the surface of the CZ-3 composite. Spillover hydrogen and oxygen vacancy could promote the formate and methoxy routes over PdCu/CZ-3, the primary intermediates producing MeOH. PdCu/CZ-3 displayed the highest CO2 conversions (25.5 %), highest MeOH yield (6.4 %), highest PdCu-TOFMeOH (7.7 h-1) and superior 100 h long-term stability than those of other PdCu/CexZr1-xO2 analogs and the reference PdCu/CeO2 and PdCu/ZrO2 catalysts. Density functional theory (DFT) calculations and in situ DRIFTS were performed to investigate the CO2−MeOH hydrogenation mechanism.

Crystallographic characterization of RuX(CO)(η(3)-C(3)H(5))(JOSIPHOS), where X = Cl, Br, I, reveals a halide-dependent diastereomeric preference that defines metal-centered stereogenicity and, therefrom, the enantioselectivity of C-C coupling in ruthenium-catalyzed anti-diastereo- and enantioselective C-C couplings of primary alcohols with 1-aryl-1-propynes to form products of carbonyl anti-(α-aryl)allylation. Computational studies reveal a non-classical hydrogen bond between iodide and the aldehyde formyl CH bond stabilizes the favored transition state for carbonyl addition. An improved catalytic system enabling previously unattainable transformations was developed that employs an iodide-containing precatalyst RuI(CO)(3)(η(3)-C(3)H(5)) in combination with trifluoroethanol (TFE), as illustrated by the first enantioselective ruthenium-catalyzed C-C couplings of ethanol to form higher alcohols.

We acknowledge the financial support from King AbdullahUniversity of Science and Technology (KAUST).

We are grateful for the financial support from the King Abdullah University of Science and Technology (KAUST), the Ministry of Science and Technology of Taiwan (MOST 109-2113-M-110-004), Guangxi Natural Science Foundation of China (No. 2020GXNSFAA297213), and the State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (No. CMEMR2020-A12) in China. The service of Ibex, Shaheen 2 High Performance Computing Facilities was provided by KAUST.

Well-defined and air-stable PN3–pincer manganese(II) complexes were synthesized and used for the hydrogenation of aldehydes into alcohols under mild conditions using MeOH as a solvent. This protocol is applicable for a wide range of aldehydes containing various functional groups. Importantly, α,β-unsaturated aldehydes, including ynals, are hydrogenated with the CC double bond/CC triple bond intact. Our methodology was demonstrated for the conversion of biomass derived feedstocks such as furfural and 5-formylfurfural to furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol respectively.

Redox driven C–C bond formation has gained recent attention over the traditional sequence of oxidative addition, insertion and reductive elimination reactions. In this regard, the transient radical mediated diverse reactivity profile of bis(heterocyclo)methanes (H–BHM: HL1–HL4) has been demonstrated as a function of varying metal ions and ligand backbones. It highlighted the following events: (a) redox induced homocoupling of deprotonated HL1 and HL4 on coordination to M(OAc)2 precursors (M = CuII, ZnII, PdII, AgI), including the effective role of molecular oxygen in the transformation process; (b) steric inhibition of C–C coupling of HL1 or HL4 on inserting the substituent at the bridged methylene centre (Ph in HL2 or CH3 in HL3); (c) competitive C–C coupling versus oxygenation of free HL1 with varying concentrations of PdII(OAc)2 as the ease of oxygenation over dimerisation of the deprotonated HL1 was corroborated by the DFT calculated lower activation barrier and greater thermodynamic stability of the former; and (d) redox non-innocence of BHMs on a coordinatively inert ruthenium platform, which in turn favored the involvement of a radical pathway for the aforestated coupling or oxygenation process. A combined structural, spectroscopic and DFT calculated transition state analysis demonstrated the mechanistic outline for the metal assisted oxidative coupling of BHMs.

Formic acid has been proposed as a hydrogen energy carrier because of its many desirable properties, such as low toxicity and flammability, and a high volumetric hydrogen storage capacity of 53 g H2 L−1 under ambient conditions. Compared to liquid hydrogen, formic acid is thus more convenient and safer to store and transport. Converting formic acid to power has been demonstrated in direct formic acid fuel cells and in dehydrogenation reactions to supply hydrogen for polymer electrolyte membrane fuel cells. However, to enable a complete cycle for the storage and utilization of low-carbon or carbon-free electricity, processes for the hydrogenation and electrochemical reduction of carbon dioxide (CO2) to formic acid, namely power to formic acid, are needed. In this review, representative homogenous and heterogeneous catalysts for CO2 hydrogenation will be summarized. Apart from catalytic systems for CO2 hydrogenation, a wide range of catalysts, electrodes, and reactor systems for the electrochemical CO2 reduction reaction (eCO2RR) will be discussed. An analysis for practical applications from the engineering viewpoint will be provided with concluding remarks and an outlook for future challenges and R&D directions.

Seawater contains significantly larger quantities of lithium than is found on land, thereby providing an almost unlimited resource of lithium for meeting the rapid growth in demand for lithium batteries. However, lithium extraction from seawater is exceptionally challenging because of its low concentration (∼0.1–0.2 ppm) and an abundance of interfering ions. Herein, we creatively employed a solid-state electrolyte membrane, and design a continuous electrically-driven membrane process, which successfully enriches lithium from seawater samples of the Red Sea by 43 000 times (i.e., from 0.21 to 9013.43 ppm) with a nominal Li/Mg selectivity >45 million. Lithium phosphate with a purity of 99.94% was precipitated directly from the enriched solution, thereby meeting the purity requirements for application in the lithium battery industry. Furthermore, a preliminary economic analysis shows that the process can be made profitable when coupled with the Chlor-alkali industry.

Water oxidation is a primary step in natural as well as artificial photosynthesis to convert renewable solar energy into chemical energy/fuels. Electrocatalytic water oxidation to evolve O2, utilizing suitable low-cost catalysts and renewable electricity, is of fundamental importance considering contemporary energy and environmental issues, yet it is kinetically challenging owing to the complex multiproton/electron transfer processes. Herein, we report the first cobalt-based pincer catalyst for catalytic water oxidation at neutral pH with high efficiency under electrochemical conditions. Most importantly, ligand (pseudo)aromaticity is identified to play an important role during electrocatalysis. A significant potential jump (∼300 mV) was achieved toward a lower positive value when the aromatized cobalt complex was transformed into a (pseudo)dearomatized cobalt species. The dearomatized species catalyzes the water oxidation reaction to evolve oxygen at a much lower overpotential (∼340 mV) on the basis of the onset potential (at a current density of 0.5 mA/cm2) of catalysis at pH 10.5, outperforming other Co-based molecular catalysts reported to date. These observations may provide a new strategy for the judicious design of earth-abundant transition-metal-based water oxidation catalysts.

A radical-based asymmetric olefin difunctionalization strategy for rapidly forging all-carbon quaternary stereocenters α to diverse azaarenes is reported. Under cooperative photoredox and chiral Bronsted acid catalysis, cyclopropylamines with α-branched 2-vinylazaarenes can undergo a sequential two-step radical process, furnishing various valuable chiral azaarene-substituted cyclopentanes. The use of the rigid and confined C2-symmetric imidodiphosphoric acid catalysts achieves high enantio- and diastereo-selectivities for these asymmetric [3 + 2] cycloadditions.

We present the mechanistic understanding of an electrochemically-driven nickel-catalyzed coupling reaction. Computational analysis reveals that the spin density is mostly residing on the nickel (Ni) center when NiII is reduced to NiI. Ni-mediated halogen atom abstraction through outer-sphere electron-transfer pathway to yield coupling products under mild conditions is demonstrated. Importantly, we have elucidated the role of NiI and Ni0 for successive coupling of benzyl bromide and benzyl chloride derivatives, respectively, to corresponding bibenzyl products. The Ni-catalyst bearing a PN3P-ligand is an effective catalyst, producing a strong ligand effect on the reactivity and selectivity for the homocoupling reactions.

Professor Yu Han is acknowledged for insightful review and discussions. We are grateful for financial support from King Abdullah University of Science and Technology (KAUST).

A novel dendritic composite (TD) with an open center-radial pore structure using TS-1 nanocrystals as microporous precursors was successfully synthesized by a facile method. TS-1 nanocrystals were embedded into the framework of dendritic mesoporous silica nanospheres (DMSNs) to form Si–O–Ti bonds, which was beneficial for generating more S vacancies of MoS2 active phases. The NiMo/TD-2 catalyst had a larger surface area and stronger metal–support interaction, resulting in higher sulfidation and dispersion degrees of MoS2 active phases over the sulfided NiMo/TD-2 catalyst, which was consequently favored to improve the hydrodesulfurization (HDS) activity of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). Furthermore, the NiMo/TD-2 catalyst with an SiO2/TiO2 molar ratio of 150 exhibited higher HDS performance for DBT and 4,6-DMDBT than other NiMo/TD catalysts and the commercial NiMo/Al2O3 catalyst. Moreover, the NiMo/TD-2 catalyst possessed more Bronsted and Lewis acid sites, thus promoting the hydrogenation of DBT and the isomerization of 4,6-DMDBT.

Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5-aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary and secondary anilines, indoline, and benzylamines are suitable amines. The weakly donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for stereoselective anti attack of amines. Agency for Science, Technology and Research (A*STAR) Economic Development Board (EDB) Accepted version We acknowledge financial support from Peking UniversityShenzhen Graduate School, Shenzhen Bay Laboratory(21230011-Scripps), Nanyang Technological University,GSK-EDB Trust Fund (2017 GSK-EDB Green and Sustain-able Manufacturing Award) and A*STAR Science andEngineering Research Council (AME IRG A1783c0010).

FeCuCo over aluminum oxide catalyst was prepared to catalytically degrade polystyrene (PS) into ethylbenzene (EB) under mild conditions. This catalyst was characterized by XRD, SEM, STEM-EELS, STEM-EDS, XPS, and physical properties. A significant selectivity toward EB formation at 250 °C was achieved in the absence of hydrogen with 82% liquid yield. End-chain session and cross-linking reactions are proposed to be the dominant pathways in the degradation of PS over FeCuCo to form EB. Keywords: Polystyrene, Catalytic-degradation, Ethylbenzene, Selective-conversion

V-substituted polymolybdenum phosphoric acid (PVxMo) supported on mesoporous silica was prepared and investigated as a catalyst for the oxidation of glycerol to formic acid in a batch operation. Different synthetic methods for PVxMo supported on mesoporous silica were compared. Detailed characterizations of the final products were carried out by N2 adsorption and desorption, XRD, HR-TEM, SEM, ICP-OES, XANES, NH3-TPD, and FTIR to identify the chemical properties and the porous structure of silica-supported PVxMo, as well as the strong interactions between PVxMo with the silica skeleton. These critical properties explain the bifunctionality of silica-supported PVxMo as a catalyst for the selective oxidation of glycerol to formic acid with standing stability. Keywords: Glycerol, Formic acid, SBA-15, V-substituted heteropoly acid

The advantages of two dimensional covalent organic framework membranes to achieve high flux have been demonstrated, but the capability of easy structural modification to manipulate the pore size has not been fully explored yet. Here we report the use of the Langmuir–Blodgett method to synthesize two ultrathin covalent organic framework membranes (TFP–DPF and TFP–DNF) that have a similar framework structure to our previously reported covalent organic framework membrane (TFP–DHF) but different lengths of carbon chains aiming to rationally control the pore size. The membrane permeation results in the applications of organic solvent nanofiltration and molecular sieving of organic dyes showed a systematic shift of the membrane flux and molecular weight cut-off correlated to the pore size change. These results enhanced our fundamental understanding of transport through uniform channels at nanometer scales. Pore engineering of the covalent organic framework membranes was demonstrated for the first time., Pore surface engineering of ultrathin COF membranes by introducing different lengths of alkyl chains into the skeleton, which allows us to precisely control the pore size of COF membranes for OSN applications and molecular sieving.

The ligand of an organometallic complex is typically considered as a spectator which can be modified to tune the steric and electronic properties of the coordination environment. We herein demonstarted a PN3P*Rh-CO pincer system where one of the C–H bonds of the pseudo-dearomatized pyridine ring was oxidized by O2 at room temperature to create an α,β-unsaturated carbonyl functionality on the ligand backbone. The resulting metal complex with the post-modified PN3P ligand readily reacts with thiophenol and 4-methylaniline to afford the corresponding oxidative Michael addition products.

The authors express their gratitude for the service of Ibex and Shaheen 2 High-Performance Computing Facilities as well as the continued financial support from King Abdullah Univ. of Science and Technology (KAUST).

Advances in processing capabilities of computer clusters have allowed for the full modeling of organometallic complexes that previously would have been simplified to reduce computational cost. Increased feasibility of computational modeling offers new challenges, not only in terms of limitations of methods and theory, but attention should be paid to complexes that can exist in many conformations, as the appropriate choice of conformer may be easily overlooked. In this work a series of pincer complexes with isopropyl and cyclopentyl substituents have been chosen as examples to demonstrate the importance of conformational analysis. The complexes examined contain four isopropyl or cyclopentyl groups on phosphor atoms generating between 27 and 324 possible rotamers. The importance of conformational search in a mechanistic investigation is demonstrated with the CO2 insertion into a nickel hydride bond of POCOP iPr nickel hydride complex. Results show that the reaction energy profile can be both exergonic and endergonic depending on rotamer choice. Specifically, the POCOPiPr Ni-formato complex product of the CO2 insertion reaction had an energy difference between the lowest and highest energy rotamer as high as 16.8 kcal/mol. The significant energy differences between rotamers highlight the importance of thorough conformational analysis and should be taken into consideration when evaluating the energy profile of related reactions. Keywords: Conformational analysis, DFT, Pincer, Mechanism, Rotamers

Gastrointestinal stromal tumors (GISTs) are prototypes of stem cell factor receptor (c-KIT)-driven cancer. Two receptor tyrosine kinases, c-KIT and fms-tyrosine kinase (FLT3), are frequently mutated in acute myeloid leukemia (AML) patients, and these mutations are associated with poor prognosis. In this study, we discovered a multitargeted tyrosine kinase inhibitor, compound 15a, with potent inhibition against single or double mutations of c-KIT developed in GISTs. Moreover, crystal structure analysis revealed the unique binding mode of 15a with c-KIT and may elucidate its high potency in inhibiting c-KIT kinase activity. Compound 15a inhibited cell proliferation and induced apoptosis by targeting c-KIT in c-KIT-mutant GIST cell lines. The antitumor effects of 15a were also demonstrated in GIST430 and GIST patient-derived xenograft models. Further studies demonstrated that 15a inhibited the proliferation of c-KIT- and FLT3-driven AML cells in vitro and in vivo. The results of this study suggest that 15a may be a potential anticancer drug for the treatment of GISTs and AML.

High-pressure H2 was produced by the selective dehydrogenation of formic acid (DFA) using ruthenium complexes at mild temperatures in various organic solvents and water. Among the solvents studied, 1,4-dioxane was the best candidate for this reaction to generate high gas pressure of 20 MPa at 80 °C using the Ru complex having a dearomatized pyridine-based pincer PN3P* ligand. This complex shows reusability for the high-pressure DFA in 1,4-dioxiane while maintaining the catalytic performance, however, deactivation occurred in other solvents. In dimethyl sulfoxide, its decomposition products may cause catalytic deactivation. The gas pressure generated in 1,4-dioxane was lower than that in water due to the high dissolution of 1,4-dioxane into CO2 according the vapor-liquid equilibrium calculations. The role of solvent is crucial since it affected the catalytic performance and also the generated gas pressure (H2 and CO2) from FA.

Formic acid possesses many desirable properties as a promising hydrogen energy carrier. Density functional theory (DFT) was utilized to design new Rh complexes with 2,2′-biimidazoline ligands to explore their potential as catalysts for formic acid dehydrogenation. These designed complexes were prepared and examined as catalysts under various temperatures and ratios of formic acid to sodium formate. It was found that although our complexes gave a high TOF of 20,000 h−1 at 90 °C under certain formic acid/sodium formate ratios, the dehydrogenation reaction was prematurely deactivated once 30% of the formic acid was consumed. Possible deactivation mechanisms were investigated by NMR and HRMS. Our observations suggest that while guided rational design of catalysts by DFT has much potential, the method does have limitations as evidenced by our experimental comparisons and thus pure DFT design should be conducted with caution.

Copper (Cu) nanocomposite catalysts with gallium (Ga) and aluminum (Al) were prepared using the simultaneous co-precipitation digestion method. The catalysts were characterized by N2 adsorption, N2...

The chemistry of anilido phosphine complexes has been popularized since 2003 when N-arylation of the parent o-anilinophosphine was made possible. This Highlight Review summarizes the cumulative pro...

A simple and low-cost polymer-aided sol–gel method was developed to prepare γ-Al2O3 protective layers for LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode materials. The selected polyvinyl alcohol polymer additive not only facilitates the formation of a uniform and thin γ-Al2O3 layer on the irregular and rough cathode particle surface to protect it from corrosion but also serves as a pore-forming agent to generate micropores in the film after sintering to allow fast transport of lithium ions, which guaranteed the excellent and stable battery performance at high working voltage. Detailed studies in the full battery mode showed that the leached corrosion species from the cathode had a more profound harmful effect to the graphite anode, which seemed to be the dominating factor that caused the battery performance decay.

Defect engineering of metal-organic frameworks (MOFs) offers promising opportunities for tailoring their properties to specific functions and applications. However, determining the structures of defects in MOFs-either point defects or extended ones-has proved challenging owing to the difficulty of directly probing local structures in these typically fragile crystals. Here we report the real-space observation, with sub-unit-cell resolution, of structural defects in the catalytic MOF UiO-66 using a combination of low-dose transmission electron microscopy and electron crystallography. Ordered 'missing linker' and 'missing cluster' defects were found to coexist. The missing-linker defects, reconstructed three-dimensionally with high precision, were attributed to terminating formate groups. The crystallization of the MOF was found to undergo an Ostwald ripening process, during which the defects also evolve: on prolonged crystallization, only the missing-linker defects remained. These observations were rationalized through density functional theory calculations. Finally, the missing-cluster defects were shown to be more catalytically active than their missing-linker counterparts for the isomerization of glucose to fructose.

The dearomatization of 3-nitroindoles through a chiral-phosphine-mediated [3+2] annulation reaction is described. This method makes use of readily available 3-nitroindoles as an aromatic feedstock and rapidly delivers a wide range of cyclopentaindoline alkaloid scaffolds in a highly enantioselective manner. Notably, phosphine-triggered cyclization has not been utilized previously in a dearomatization process.

Tremendous research efforts have been made to electrochemically convert CO2 into useful chemicals, with the main products being limited to hydrocarbons and oxygenates. One-step processes that integ...

Iridium complexes modified by PhanePhos catalyze the 2-propanol-mediated reductive coupling of diverse 1,1-disubstituted allenes 1a-1u with fluoral hydrate 2a to form CF(3)-substituted secondary alcohols 3a-3u that incorporate acyclic quaternary carbon-containing stereodiads. By exploiting concentration-dependent stereoselectivity effects related to the interconversion of kinetic (Z)- and thermodynamic (E)-σ-allyliridium isomers, adducts 3a-3u are formed with complete levels of branched regioselectivity and high levels of anti-diastereo- and enantioselectivity. The utility of this method for construction of CF(3)-oxetanes and CF(3)-azetidines is illustrated by the formation of 4a and 6a, respectively. Studies of the reaction mechanism aimed at illuminating the singular effectiveness of PhanePhos as a supporting ligand in this and related transformations have led to the identification of a chromatographically stable cyclometallated iridium-(R)-PhanePhos complex Ir-PP-I that is catalytically competent for allene-fluoral reductive coupling and previously reported transfer hydrogenative C-C couplings of dienes or CF(3)-allenes with methanol. Deuterium labelling studies, reaction progress kinetic analysis (RPKA) and computational studies corroborate a catalytic mechanism involving rapid allene hydrometalation followed by turnover-limiting carbonyl addition. A computationally determined stereochemical model shows the ortho-CH(2) group of the cyclometallated iridium-PhanePhos complex plays a key role in directing diastereo- and enantioselectivity. The collective data provide key insights into the structural-interactional features of allyliridium complexes required to enforce nucleophilic character, which should inform the design of related cyclometallated catalysts for umpoled allylation.

A PN3P pincer ligand (1) bearing dicyclopentylphosphine substituents reacts with [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) to produce the complex (PN3P)RhCl (2). Treatment of a benzene solution of 2 with KN(SiMe3)2 stimulates a dearomatization process, and C–H activation of benzene is achieved through the rearomatization of the central pyridine ring. This deprotonation/reprotonation of the NH arm of 2 gives the phenyl complex (PN3P)Rh(C6H5) (3). The subsequent introduction of CO gas into 3 yields the benzoyl complex (PN3P)RhCO (C6H5) (4), which can release benzaldehyde upon treatment with diluted HCl solution and regenerates 2.

H2 heterolysis to generate well-defined nickel hydride-proton complexes was achieved by the 2nd generation PN3P-pincer nickel platform. The regioselective protonation in the ligand framework was demonstrated for the first time to highlight the importance of in-plane hindrance during the H2 splitting process.

PN3P-Ir pincer hydride complexes were synthesized and characterized as catalysts and key intermediates in the direct hydrogenation of CO2 to formate under mild conditions. The formation of a dearomatized PN3P*-Ir(i)-CO species was identified as a plausible key process accountable for the loss of catalytic activity in the CO2 hydrogenation.

The production of 1-butene by ethylene dimerization is an important chemical industrial process currently implemented using homogeneous catalysts. Here, we describe a highly active heterogeneous catalyst (Ni-ZIF-8) for ethylene dimerization, which consists of isolating Ni-active sites selectively located on the crystal surface of a zeolitic imidazolate framework. Ni-ZIF-8 can be easily prepared by a simple one-pot synthesis method in which site-specific anchoring of Ni is achieved spontaneously because of the incompatibility between the d8 electronic configuration of Ni2+ and the three-dimensional framework of ZIF-8. The full exposure and square-planar coordination of the Ni sites accounts for the high catalytic activity of Ni-ZIF-8. It exhibits an average ethylene turnover frequency greater than 1 000 000 h-1 (1-butene selectivity >85%) at 35 °C and 50 bar, far exceeding the activities of previously reported heterogeneous catalysts and many homogeneous catalysts under similar conditions. Moreover, compared to molecular Ni complexes used as homogeneous catalysts for ethylene dimerization, Ni-ZIF-8 has significantly higher stability and shows constant activity during 4 h of continuous reaction. Isotopic labeling experiments indicate that ethylene dimerization over Ni-ZIF-8 follows the Cossee-Arlman mechanism, and detailed characterizations combined with density functional theory calculations rationalize this observed high activity.

Unlike the conventional model of transition metal catalysis, ligands in metal-ligand cooperative (or bifunctional) catalysis are involved in the substrate activations. Such processes have offered unique mechanistic understandings and led to new concepts for the catalyst design. In particular, unprecedented activities were discovered when the ligand could undergo dearomatization-rearomatization reactions during the catalytic cycle. Aromatization can provide an extra driving force to thermodynamics; consequently, it brings a new perspective to ligand platform design for catalysis. While numerous applications were demonstrated, the influences of changing ligand aromatic properties were often overlooked. In this article, representative ligand systems will be highlighted and a comparison between the Milstein and the Huang pincer systems will be discussed to provide theoretical and conceptual insights.

Selective conversion of CO2 to formate with high current densities is highly desirable but still challenging. Copper hollow fibers with interconnected pore structures were fabricated via a facile method and used as a stand-alone cathode for highly efficient electrochemical reduction of CO2 to formate. Our studies revealed that delivering the reactant CO2 gas to the inner space of the hollow fiber could build up a higher CO2 partial pressure in the pores and presumably reduce the concentration of H[Formula: see text] from the electrolyte to effectively suppress the major competing reaction, hydrogen evolution reaction (HER), from 46.9% faradaic efficiency (FE) to 15.0%. A high selectivity for CO2 reduction to formate with a maximum FE of 77.1% was achieved with a high current density of 34.7[Formula: see text]mA cm[Formula: see text], which is one of the highest FEs on Cu-based materials. Mechanistic studies suggest that the abundant active sites along with the unique crystal facets induced by the high pressure of CO2 at the pore surface in the “gas in” mode are attributed to the superior electroactivity and selectivity for the CO2 reduction to formate. The Cu hollow fiber electrodes exhibit an outstanding long-term stability at high current density, showing great potential for large-scale practical applications.

Formic acid is considered as a promising hydrogen energy carrier due to its high volumetric hydrogen capacity of 53 g H2/L under ambient conditions, and its low toxicity and flammability. It is thus safe and convenient to store and transport formic acid. Particularly in the last 15 years or so, tremendous progress was witnessed in both utilisation and generation of formic acid. In this chapter, important developments that could potentially utilise low-carbon or carbon-free electricity in both hydrogenation and electrochemical reduction of carbon dioxide for formate/formic acid synthesis will be discussed. Conclusive remarks about the future challenges and opportunities will be provided in the end.

Novel dendritic micro-mesoporous TS-1/dendritic mesoporous silica nanoparticle (DMSN) composites (TD) were assembled by TS-1 nanocrystals with ultrasmall particle size and strong acidity. TS-1 seeds and DMSNs were composited via the Ti-O-Si chemical bond, which stimulate the generation of Bronsted (B) and Lewis (L) acids. The spillover d-electrons produced by the Ti element of TS-1 seeds produced a spillover of d-electrons, which could interact with the surface of MoS2 phases, thereby reducing Mo-S interactions and create sulfur vacancies that are favorable for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions. The increased amount of B&L acid of NiMo/TD-2.0 with cetyltrimethylammonium bromide/sodium salicylate molar ratio of 2.0 played an important role in facilitating the hydrogenation (HYD) route of DBT HDS and the isomerization (ISO) route of 4,6-DMDBT HDS, which is more favorable for the reduction of steric hindrance of DBT and 4,6-DMDBT reactants in the HDS reaction process. The NiMo/TD-2.0 catalyst exhibited the highest turnover frequency (TOF) value and HDS reaction rate constant (kHDS) of DBT and 4,6-DMDBT due to its ultrasmall particle size, uniform spherical dendritic morphology, strong B&L acidity, and good stacking degree.

The molecular structure of a catalytically active key intermediate is determined in solution by employing 2D IR spectroscopy measuring vibrational cross-angles. The formate intermediate (2) in the formic acid dehydrogenation reaction catalyzed by a phosphorus–nitrogen PN(3)P–Ru catalyst is elucidated. Our spectroscopic studies show that the complex features a formate ion directly attached to the Ru center as a ligand, and a proton added to the imine arm of the dearomatized PN(3)P* ligand. During the catalytic process, the imine arms are not only reversibly protonated and deprotonated, but also interacting with the protic substrate molecules, effectively serving as the local proton buffer to offer remarkable stability with a turnover number (TON) over one million.

In contrast to the conventional strategy of modifying the reactivities and selectivities of the transition metal and organocatalysts by varying the steric and electronic properties of organic substituent groups, we hereby demonstrate a novel approach that the sigma (σ) nucleophilicity of the imine arm can be significantly enhanced in a pseudodearomatized PN3P* pincer ligand platform to reach unprecedented N-heterocyclic carbene-like reactivity. Accordingly, the imine arm of the PN3P*Ni-H pincer complex efficiently catalyzes the hydrosilylation of aldehydes, cycloaddition of carbon dioxide (CO2) to epoxides, and serves as a ligand in the Ru-catalyzed dehydrogenative acylation of amines with alcohols.

We gratefully acknowledge the financial support from King Abdullah University of Science and Technology; Competitive Research Grant (URF/1/1378) and Baseline Funding, and from Chinese NSFC (51672309) and the Fundamental Research Funds for the Central Universities (18CX07009A).

Two-dimensional (2D) covalent organic framework (COF) materials have the most suitable microstructure for membrane applications in order to achieve both high flux and high selectivity. Here, we report the synthesis of a crystalline TFP-DHF 2D COF membrane constructed from two precursors of 1,3,5-triformylphloroglucinol (TFP) and 9,9-dihexylfluorene-2,7-diamine (DHF) through the Langmuir-Blodgett (LB) method, for the first timed. A single COF layer is precisely four unit cells thick and can be transferred to different support surfaces layer by layer. The TFP-DHF 2D COF membrane supported on an anodic aluminum oxide (AAO) porous support displayed remarkable permeabilities for both polar and nonpolar organic solvents, which were approximately 100 times higher than that of the amorphous membranes prepared by the same procedure and similar to that for the best of the reported polymer membranes. The transport mechanism through the TFP-DHF 2D COF membrane was found to be a viscous flow coupled with a strong slip boundary enhancement, which was also different from those of the amorphous polymer membranes. The membrane exhibited a steep molecular sieving with a molecular weight retention onset (MWRO) of approximately 600 Da and a molecular weight cutoff (MWCO) of approximately 900 Da. The substantial performance enhancement was attributed to the structural change from an amorphous structure to a well-defined ordered porous structure, which clearly demonstrated the high potential for the application of 2D COFs as the next generation of membrane materials.

The transition metal-catalyzed reductive cyclization of o-nitrostyrene in the presence of carbon monoxide (CO) has been developed to be a general synthetic route to an indole skeleton, wherein CO w...

Formic acid (FA) has been extensively studied as one of the most promising hydrogen energy carriers today. The catalytic decarboxylation of FA ideally leads to the formation of CO2 and H2 that can be applied in fuel cells. A large number of transition-metal based homogeneous catalysts with high activity and selectivity have been reported for the selective FA dehydrogentaion. In this review, we discussed the recent development of C,N/N,N-ligand and pincer ligand-based homogeneous catalysts for the FA dehydrogenation reaction. Some representative catalysts are further evaluated by the CON/COF assessment (catalyst on-cost number)/(catalyst on-cost frequency). Conclusive remarks are provided with future challenges and opportunities.

The aim of this work is to prepare catalysts for energy efficient conversion of polystyrene (PS) and its waste into valuable products with high conversion at 250 °C. The FeCo/Alumina bimetallic catalyst was synthesized by aqueous impregnation and structurally determined using scanning-transmission electron microscopy, temperature programmed desorption, X-ray diffraction, and X-ray photoelectron spectroscopy. Successfully, we have achieved up to 91% liquid yield with selectivities for styrene monomer (SM) up to 45 wt% and ethylbenzene (EB) up to 55 wt%, depending on the exposure time at 250 °C by FeCo/Alumina which is comparable to those of reactions at high temperatures (≥350 °C). Further increase of catalyst loadings from 200 to 400 mg also led to the decrease in styrene yield and increase in ethylbenzene yield. The analysis of the resulting clear liquid by gas chromatography/mass spectrometry (GC/MS) indicates the generation of products in the gasoline range.

The catalytic activity of iron(II) complexes with functionalized amine-pyrazolyl tripodal ligands toward dimerization of terminal alkynes in the presence a base (KOtBu or NaOtBu) has been studied. An unusual E/Z selectivity of the reaction determined by tert-butoxide was observed.