The formylation and methylation of amines with carbon dioxide hydrosilanes are emerging yet important types transformations for CO2. Catalytic methods effective both reactions wide substrate scopes rare because the difficulty in controlling selectivity. Herein, we report that simple readily available inorganic bases—alkali-metal carbonates, especially cesium carbonate—catalyze efficiently under mild conditions. selectivity can be conveniently controlled by varying reaction temperature...

One-step conversion of low-purity polyolefins to value-added products without pretreatments represents a great opportunity for chemical recycling waste plastics. However, additives, contaminants, and heteroatom-linking polymers tend be incompatible with catalysts that break down polyolefins. Here, we disclose reusable, noble metal-free impurity-tolerant bifunctional catalyst, MoSx-Hbeta, hydroconversion into branched liquid alkanes under mild conditions. The catalyst works wide scope...

Recently, metal-mediated electrochemical conversion of nitrogen and hydrogen to ammonia (M-eNRRs) has been attracting intense research attention as a potential route for synthesis under ambient conditions. However, which metals should be used mediate M-eNRRs remains unanswered. This work provides an extensive comparison the energy consumption in classical Haber Bosch (H-B) process M-eNRRs. The results indicate that when employing lithium calcium, popularly M-eNRRs, is more than 10 times...

The introduction of bulky ammoniums into methyl ammonium lead iodide hybrid perovskites (MAPbI 3 ) has emerged as a promising strategy to improve the properties these materials. In present work, we studied effects several aromatic onto structural, electronic, and optical MAPbI . Although powder XRD data suggest that cations are not involved in bulk phase , surprisingly large effect photoluminescence was observed.

We report a Ni1Ru1/C catalyst with downshifted d-band center due to the presence of RuO 2 /NiRu heterogeneous interface, which appropriately weakens too-strong adsorption H* and thus improved HER performance.

Here we report the formation of first examples dicopper(III) bis(μ-oxo) complexes ligated by primary amines, propylenediamine, and N,N,-dimethyl propylenediamine. Stabilization these new compounds is effected at −125 °C "core capture"— introduction exogenous ligand to a preformed complex supported peralkylated tetramethyl Primary amine ligation in matches single coordination putative active site particulate methane monooxygenase (pMMO) polysaccharide monooxygenase. Reactivity studies...

Artificial photosynthetic systems store solar energy in chemical fuels <italic>via</italic> CO₂ reduction or renewable hydrogen evolution from water splitting.

With NaBH 4 as the assistant reductant, small and highly dispersed Pt nanoparticles are formed on E-MoS 2 nanosheets which provide abundant catalytically active sites exhibit excellent hydrogen evolution reaction (HER) performance.

Electroreduction of CO2 to ethanol remains a formidable challenge due the unsatisfactory efficiency C–C coupling process and demand for complex oxygen-containing intermediates, thus resulting in poor selectivity electrocatalytic activity. Cu–Ag bimetallic materials with adjustable electronic structures active site exposure are promising catalysts electrochemically convert ethanol. Herein, we report Ag-decorated Cu2O promote catalytic performance electroreduction The as-prepared CuAg-0.75%...

Several pyridine-like ligands were found to improve Pd(OAc) 2 -catalyzed allylic oxidation of allylbenzene cinnamyl acetate by p-benzoquinone in acetic acid. The best ligand examined, bipyrimidine, was used identify the catalyst precursor for this system, (bipyrimidine)Pd(OAc) , which fully characterized. Mechanistic studies suggest reaction takes place through disproportionation form a bipyrimidine-bridged dimer, reacts with olefin Pd II -olefin adduct, followed C–H activation produce (η 3...

Copper thiolate/disulfide interconversions are related to the functions of several important proteins such as human Sco1, Cu-Zn superoxide dismutase (SOD1), and mammalian zinc-bonded metallothionein. The synthesis characterization well-defined synthetic analogues for challenging yet provide insights into mechanisms redox processes. Solvent-dependent isomerization proton-coupled electron transfer mimicking these observed in two structurally dimeric μ,η(2):η(2)-thiolato Cu(II)Cu(II) complexes...

Platinum(II) and palladium(II) complexes are well-known to catalyze the partial oxidation of alkanes. Herein, we present experimental evidence that tunneling occurs in protonolysis M(II)-CH(3) (M = Pt, Pd) model systems. We propose there may be a connection between observation mechanism involving direct protonation M-C bond also expected for electrophilic C-H activation methane by Pt(II) Pd(II) proceeds via proton loss from sigma complex.

The protonolysis of platinum(II) and palladium(II) methyl complexes has been investigated by both experiment computation. Previously the (COD)PtII(CH3)2 CF3COOY or (dppe)PdII(CH3)2 CF3CY2OY (Y = H, D) was found to be accompanied abnormally large highly temperature-dependent kinetic isotope effects (KIEs), suggesting involvement tunneling. Here we find normal KIEs no evidence tunneling for (tmeda)PtII(CH3)Cl D). Density functional theory (DFT) calculations indicate that protonation at metal...

Making polymers from CO2 and olefins has been long sought is of particular significance for chemical utilizations CO2. Herein, high molecular-weight with 29 wt % were obtained by polymerizing a δ-lactone (L) synthesized C-C coupling reaction between 1,3-butadiene, an economical large-volume that can also be derived top biomass platform chemicals. Although L known many years, little was investigated in its polymerization. We found L's polymerizability vitalized upon simply heating the...

Two-dimensional transition-metal dichalcogenides are affordable alternatives to noble metal catalysts for hydrogen evolution reaction (HER). Here, we report a facile one-step solvothermal method synthesize the 1T MoS2 hierarchical nanosphere (NSP) that can function as an efficient and stable electrocatalyst HER using environment-friendly solvent without assistance of template or additive. The is found play vital role in regulating morphology phase resultant MoS2. A haystack 2H nanosheets...

Abstract Synthesis of monomer‐recyclable polyesters solely from CO 2 and bulk olefins holds great potential in significantly reducing emissions addressing the issue plastic pollution. Due to kinetic disadvantage direct copolymerization compared homopolymerization olefins, considerable research attention has been devoted synthesis polyester via ring‐opening polymerization (ROP) a six‐membered disubstituted lactone intermediate, 1,2‐ethylidene‐6‐vinyl‐tetrahydro‐2H‐pyran‐2‐one ( 𝜹‐L ),...

Abstract Synthesizing chemically recyclable solid polymeric materials is a significant strategy to potentially achieve carbon neutral production of new polymers and alleviate plastic pollution, especially when the synthesis based on CO 2 inexpensive co‐feedstocks available in large scales. Additionally, should have high enough molecular weight exhibit distinguished properties from low molar mass serve for broader range application scenarios. However, up now, strategies developing solid‐state...

The non-spectator roles of NHC ligands have attracted wide attention due to their important implications for reaction mechanisms and subsequent impact on catalyst design. Herein, we report facile Ccarbene−halogen reductive eliminations from copper halide complexes at RT under oxidative conditions. Density functional calculations a simplified model system suggest that the reactions occur through oxidation Cu(I) species Cu(III) followed by complexes. Remarkably short Ccarbene−chloride contacts...