Herringtobin4775

Controlled generation of homoleptic versus heteroleptic AuI2M (M = NiII, ZnII) trinuclear complexes, which is achieved by a slight change in the diphosphine P^P linker of digold(i) metalloligands, [Au2(P^P)(d-pen)2]2- (L1P^P; d-pen = d-penicillaminate) and [Au2(P^P)(l-cys)2]2- (L2P^P; l-cys = l-cysteinate), is reported. The reactions of a 1  1 mixture of L1dppm and L2dppm (dppm = bis(diphenylphosphino)methane) with M = NiII, ZnII gave the homoleptic AuI2M complexes, [M(L1dppm)] and [M(L2dppm)], which co-crystallized to form [M(L1dppm)]·[M(L2dppm)] (1M). Similar reactions using L1dppe and L2dppe (dppe = bis(diphenylphosphino)ethane), instead of L1dppm and L2dppm, led to the selective production and crystallization of the heteroleptic AuI2M complex, [M(L3dppe)] (2M; L3dppe = [Au2(dppe)(l-cys)(d-pen)]2-), accompanied by the scrambling of L1dppe and L2dppe. The homoleptic 1M and the heteroleptic 2M showed different absorption (green versus blue) and emission (yellow versus orange) colours for M = NiII and ZnII, respectively.A cross-linked π-conjugated polymeric cobalt phthalocyanine material was developed by a facile, economical, scalable, and solid-phase synthesis method. In addition to being highly recyclable, this material showed greatly enhanced activity for the aerobic oxidative coupling of amines compared with a molecular catalyst before heterogenization, indicating good prospects for the material with a π-conjugated electronic character.Exploring two-dimensional anode materials that can utilize the storage capacity and diffusion mobility of Li ions is at the heart of lithium ion battery (LIB) research. Herein, we report the results of ab initio electronic structure calculations on the storage capacity and diffusion mobility affinities of Li ions adsorbed onto nondefective and defective MXene V2C monolayers. It is found that Li ions strongly chemisorb on the two sides of the V2C surface with a preferential adsorption site at the hollow center of the honeycomb structure. The binding profile and open-circuit voltage calculations reveal that the Li/V2C structure exhibits a specific capacity as high as 472 mA h g-1 at the Li2V2C stoichiometry, a value relatively high compared with those of the typical anode materials including graphite (372 mA h g-1). Furthermore, the diffusion barrier of a Li ion over the V2C surface is identified to be no more than 0.1 eV, which is a few times smaller than that of graphene and graphitic anodes. In addition, during the lithiation and delithiation processes, the change in the lateral lattice is quite small, only about a 2% increase at the full lithiation of Li2V2C, implying a good cycling performance. Importantly, these intriguing findings are very robust against the intrinsic structural and atomic defects including local point vacancies and biaxial compressive and tensile strains. More specifically, the presence of a monovanadium vacancy enhances the binding energy up to 3.1 eV per Li ion, which is about a 30% enhancement compared with the defect-free Li/V2C structure, and reduces the activation barrier by about 2 meV; meanwhile, these binding and diffusion mobility features can be improved even more when the lattice constant of the V2C monolayer is expanded. These results thus suggest that MXene V2C could be a promising anode material with high capacity and high rate capabilities for next generation high-performance LIBs.The reaction between CO and HO2 plays a significant role in syngas combustion. In this work, the catalytic effect of single-molecule water on this reaction is theoretically investigated at the CCSD(T)/aug-cc-pV(D,T,Q)Z and CCSD(T)-F12a/jun-cc-pVTZ levels in combination with the M062X/aug-cc-pVTZ level. Firstly, the potential energy surface (PES) of CO + HO2 (water-free) is revisited. The major products CO2 + OH are formed via a cis- or a trans-transition state (TS) channel and the formation of HCO + O2 is minor. In the presence of water, the title reaction has three different pre-reactive complexes (i.e., RC2 COHO2 + H2O, RC3 COH2O + HO2, and RC4 HO2H2O + CO), depending on the initial hydrogen bond formation. Compared to the water-free process, the reaction barriers of the water-assisted process are reduced considerably, due to more stable cyclic TSs and complexes. The rate constants for the bimolecular reaction pathways CO + HO2, RC2, RC3, and RC4 are further calculated using conventional transition state theory (TST) with Eckart asymmetric tunneling correction. For reaction CO + HO2, our calculations are in good agreement with the literature. learn more In addition, the effective rate constants for the water-assisted process decrease by 1-2 orders of magnitude compared to the water-free one at a temperature below 600 K. In particular, the effective rate constants for the water-assisted and water-free processes are 1.55 × 10-28 and 3.86 × 10-26 cm3 molecule-1 s-1 at 300 K, respectively. This implies that the contribution of a single molecule water-assisted process is small and cannot accelerate the title reaction.Mixed-dimensional binary heterostructures, especially 0D/2D heterostructures, have attracted significant attention due to their unique physical properties. In this contribution, 0D bismuth quantum dots (Bi QDs, VA) are immobilized onto 2D Te nanosheets (Te NSs, VIA) to prepare Bi QDs/Te NSs binary heterostructures (Bi/Te) through a facile and cost-effective hydrothermal method. The results from both experiments and density functional theory (DFT) calculations demonstrate the enhanced photo-response behaviors of Bi/Te-based photoelectrochemical (PEC)-type photodetectors (PDs). The as-prepared PDs exhibit a high photocurrent of 18.21 μA cm-2, significantly higher than those of previously reported pristine Bi QD and Te NS-based PDs. The PDs are further demonstrated to have excellent self-power capability and long-term stability over 30 days. Additionally, the obtained 786 fs pulse output signal in the telecommunications band reveals the great potential of Bi/Te for ultrafast photonic devices. It is believed that such VA/VIA binary heterostructures provide opportunities for developing multifunctional optoelectronic devices for nano-science applications.