Heterogeneous Carbonylation of Alcohols on Charge-Density-Distinct Mo-Ni Dual Sites Localized at Edge Sulfur Vacancies.

Alcohols carbonylation is of great importance in industry but remains a challenge to abandon the usage of the halide additives and noble metals. Here we report the realization of direct alcohols heterogeneous carbonylation to carbonyl-containing chemicals, especially in methanol carbonylation, with a remarkable space-time-yield (STY) of 4.74 mol/kg/h and a durable stability as long as 100 h on Ni@MoS catalyst.

Single-Pd-Site Catalyst Induced by Different Dimensional Nitrogen of N-Doping Carbon for Efficient Hydroaminocarbonylation of Alkynes.

The unsaturated amides are traditionally synthesized by acylation of carboxylic acids or hydration of nitrile compounds but are rarely investigated by hydroaminocarbonylation of alkynes using heterogeneous single-metal-site catalysts (HSMSCs). Herein, single-Pd-site catalysts supported on N-doping carbon (NC) with different nitrogen dimensions inherited from corresponding metal-organic-framework precursors are successfully synthesized. 2D NC-supported single-Pd-site (Pd/NC-2D) exhibited the best performance with near 100% selectivity and 76% yield of acrylamide for acetylene hydroaminocarbonylation with better stability, superior to those of Pd/NC-3D, single-metal-site/nanoparticle coexisting catalyst, and nanoparticle catalyst.

Water-participated mild oxidation of ethane to acetaldehyde.

The direct conversion of low alkane such as ethane into high-value-added chemicals has remained a great challenge since the development of natural gas utilization. Herein, we achieve an efficient one-step conversion of ethane to C oxygenates on a Rh/AC-SNI catalyst under a mild condition, which delivers a turnover frequency as high as 158.5 h.

Chlorine-Coordinated Unsaturated Ni-N Sites for Efficient Electrochemical Carbon Dioxide Reduction.

Heteroatom-doping is an effective method for modifying the geometric symmetry of metal-nitrogen-carbon (M-N-C) single-atom catalysts and thereby tuning the electronic structure. Up to now, most of the current reports have concentrated on introducing heteroatoms into the highly symmetrical M-N structure. The coordination-unsaturated M-N structure is more sterically favorable for the insertion of alien atoms to optimize the electronic structure.

Boron-Doped Nickel-Nitrogen-Carbon Single-Atom Catalyst for Boosting Electrochemical CO Reduction.

Tuning the coordination environment of the metal center in metal-nitrogen-carbon (M-N-C) single-atom catalysts via heteroatom-doping (oxygen, phosphorus, sulfur, etc.) is effective for promoting electrocatalytic CO reduction reaction (CO RR). However, few studies are investigated establishing efficient CO reduction by introducing boron (B) atoms to regulate the M-N-C structure.

Palladium and Ruthenium Dual-Single-Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption.

Heterogeneous single-metal-site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd -Ru single-atom-sites supported on porous ionic polymers (Pd -Ru /PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds.

Sulfur Poisoning and Self-Recovery of Single-Site Rh /Porous Organic Polymer Catalysts for Olefin Hydroformylation.

Sulfur poisoning and regeneration are global challenges for metal catalysts even at the ppm level. The sulfur poisoning of single-metal-site catalysts and their regeneration is worthy of further study. Herein, sulfur poisoning and self-recovery are first presented on an industrialized single-Rh-site catalyst (Rh /POPs).

An efficient and ultrastable single-Rh-site catalyst on a porous organic polymer for heterogeneous hydrocarboxylation of olefins.

A heterogeneous hydrocarboxylation process of olefins to obtain carboxylic acids with one more carbon was first realized using a single-Rh-site catalyst formed on porous organic polymer (Rh/POPs). The in situ formation of hydrophilic porous ionic polymer from hydrophobic POPs with the help of CHI led to high activity and superb stability.

In situ formation of mononuclear complexes by reaction-induced atomic dispersion of supported noble metal nanoparticles.

Supported noble metal nanoclusters and single-metal-site catalysts are inclined to aggregate into particles, driven by the high surface-to-volume ratio. Herein, we report a general method to atomically disperse noble metal nanoparticles. The activated carbon supported nanoparticles of Ru, Rh, Pd, Ag, Ir and Pt metals with loading up to 5 wt.

Dual-Ionically Bound Single-Site Rhodium on Porous Ionic Polymer Rivals Commercial Methanol Carbonylation Catalysts.

Novel porous polymers can serve as self-supporting solid carriers and provide abundant coordination or charged sites for single-site metals, and thus are emerging as advanced functional materials in heterogeneous catalysis for various transformations traditionally catalyzed by homogeneous systems. A brief overview of the development of this heterogenization given, including the recent advances regarding electrovalent bonds by employing charged supports represented by porous ionic polymers (PIPs), which is exemplified herein with a novel single-site Rh /PIP catalyst, featuring a new active site [Rh(CO)I ] dual-ionically bound onto a quaternary phosphonium cationic framework polymer, different from the single-ionically bound [Rh(CO) I ] in previous studies. Such a unique metal configuration of Rh /PIP leads to excellent performance in vapor-phase methanol carbonylation, outperforming commercial homo- and heterogeneous catalysts.