Structural Analysis and Intrinsic Enzyme Mimicking Activities of Ligand-Free PtAg Nanoalloys.

Nanozymes are nanomaterials with biocatalytic properties under physiological conditions and are one class of artificial enzymes to overcome the high cost and low stability of natural enzymes. However, surface ligands on nanomaterials will decrease the catalytic activity of the nanozymes by blocking the active sites. To address this limitation, ligand-free PtAg nanoclusters (NCs) are synthesized and applied as nanozymes for various enzyme-mimicking reactions. By taking advantage of the mutual interaction of zeolitic imidazolate frameworks (ZIF-8) and Pt precursors, a good dispersion of PtAg bimetal NCs with a diameter of 1.78 ± 0.1 nm is achieved with ZIF-8 as a template. The incorporation of PtAgNCs in the voids of ZIF-8 is confirmed with structural analysis using the atomic pair-distribution function and powder X-ray diffraction. Importantly, the PtAgNCs present good catalytic activity for various enzyme-mimicking reactions, including peroxidase-/catalase- and oxidase-like reactions. Further, this work compares the catalytic activity between PtAg NCs and PtAg nanoparticles with different compositions and finds that these two nanozymes present a converse dependency of Ag-loading on their activity. This study contributes to the field of nanozymes and presents a potential option to prepare ligand-free bimetal biocatalysts with sizes in the nanocluster regime.

Engineering PtCu nanoparticles for a highly efficient methanol electro-oxidation reaction.

Achieving a highly efficient and durable methanol electro-oxidation catalyst in acid media is critical for the practical utilization of direct methanol fuel cells (DMFCs) at the commercial scale. Herein, we report a facile and effective one-pot strategy for the synthesis of carbon-supported PtCu alloy nanoparticles (PtCu NPs) with a Pt-rich surface, small particle size and uniform dispersion. The as-prepared PtCu NPs with the optimal alloy composition (Pt2Cu) exhibit a significantly improved electrochemical methanol oxidation reaction performance in terms of a high activity, superior CO tolerance and remarkable durability, in contrast to those of commercial Pt/C catalysts in acid media. Particularly, the Pt2Cu/C catalyst exerts a 4.5 times enhancement in the mass activity and a larger If/Ib value compared to those of commercial Pt/C (Pt/Ccomm). The enhanced catalytic activities can be ascribed to the high utilization of Pt and the high index facets of the surface. Also, the addition of Cu downshifts the d-band center of Pt and improves the CO tolerance during the methanol oxidation reaction process. This work provides an efficient strategy for designing desired Pt-based alloys for various catalytic reactions.

Carbon-Supported Divacancy-Anchored Platinum Single-Atom Electrocatalysts with Superhigh Pt Utilization for the Oxygen Reduction Reaction.

Maximizing the platinum utilization in electrocatalysts toward oxygen reduction reaction (ORR) is very desirable for large-scale sustainable application of Pt in energy systems. A cost-effective carbon-supported carbon-defect-anchored platinum single-atom electrocatalysts (Pt1 /C) with remarkable ORR performance is reported. An acidic H2 /O2 single cell with Pt1 /C as cathode delivers a maximum power density of 520 mW cm-2 at 80 °C, corresponding to a superhigh platinum utilization of 0.09 gPt kW-1 . Further physical characterization and density functional theory computations reveal that single Pt atoms anchored stably by four carbon atoms in carbon divacancies (Pt-C4 ) are the main active centers for the observed high ORR performance.

A Bifunctional Highly Efficient FeNx /C Electrocatalyst.

Herein, a type of Fe, N-codoped carbon electrocatalyst (FeNx /C, Fe-N-BCNT#BP) containing bamboo carbon nanotubes and displaying bifunctional high catalytic efficiency for both oxygen reduction reaction (ORR) and carbon dioxide reduction reaction (CO2RR) is reported. It shows high electrocatalytic activity and stability for both the ORR process with onset potential of 1.03 VRHE in alkaline and the CO2RR to CO with high faradic efficiency up to 90% and selectivity of about 100% at low overpotential of 0.49 V. For CO2RR to CO, it is revealed that Fe3 C is active but the activity of FeNx centers is lower than that of C-N-based centers, contrary with that observed for ORR. Due to its low cost and high electrocatalytic performance for these two reduction reactions, the obtained catalyst is very promising for extensive application in future. The revealed huge activity difference of the same types of active sites for different reactions can efficiently guide the synthesis of advanced materials with multifunction.

Improving the Mechanical Properties and Tribological Behavior of Sulfobetaine Polyurethane Based on Hydrophobic Chains to Be Applied as Artificial Meniscus.

In the context of meniscus reconstruction in knee joints, current bulk biomaterials fail to meet the clinical demands for both excellent mechanical strength and low coefficient of friction. In this research, zwitterionic polyurethanes (PUs) with varying sulfobetaine (SB) groups were synthesized as the potential materials for artificial meniscus to investigate the relationship between the structures of SB groups and the performances of PUs. Under the saturation condition of 3 mg/mL hyaluronic acid aqueous solution, PU with long-alkyl chains and SB groups (PU-hSB4) exhibited a good tensile modulus (111.5 MPa) because the hydrophobic interaction of carbon chains was able to maintain the ordered aggregations of hard segment domains. Interestingly, hydrophobic chains in the molecular chain could also improve the tribological performance of PU-hSB4 instead of resulting from the surface roughness of samples, the components of lubricants, and the counterface of samples. A thicker and relatively stable hydration layer of noncrystal water was formed on the surface of PU-hSB4, which exhibited superior resistance to external forces compared to other PUs. Even if the hydration layer was damaged, PU-hSB4 was able to resist the compression of cartilage due to its high surface modulus, thus maintaining a similar and stable coefficient of friction (0.15-0.16) to native meniscus (0.18) and excellent wear resistance. In addition, the low cytotoxicity of PU-hSB4 further demonstrated its great potential to be applied in artificial meniscus instead.

catena-Poly[[[tetra-aqua-zinc(II)]-µ-4,4'-bipyridine-κN:N'] benzene-1,4-di-carboxyl-ate].

In the title compound, {[Zn(C(10)H(8)N(2))(H(2)O)(4)](C(8)H(4)O(4))}(n), the Zn(II) atoms, lying on a twofold rotation axis, are bridged by 4,4'-bipyridine ligands, resulting in a linear chain along the b axis. In the chain, the Zn(II) atom adopts a slightly distorted octa-hedral coordination geometry involving four water mol-ecules at the equatorial positions. The noncoordinated benzene-1,4-dicarboxyl-ate anion, which is also located on a twofold rotation axis, bridges adjacent chains through O-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular network.

Growth mechanism deconvolution of self-limiting supraparticles based on microfluidic system.

The synthesis of colloidal supraparticles (SPs) based on self-assembly of nanoscopic objects has attracted much attention in recent years. Here, we demonstrate the formation of self-limiting monodisperse gold SPs with core-shell morphology based on the building blocks of flexible nanoarms in one step. A flow-based microfluidic chip is utilized to slow down the assembly process of the intermediates, which surprisingly allows for observation of ultrathin gold nanoplates as first intermediates. Notably, these intermediate cannot be observed in traditional synthesis due to their rapid rolling-up to form the second-order nanostructure of flexible hollow nanoarms. The growth mechanism of SPs can then be deconvoluted into two seed-mediated steps. Monte Carlo simulations confirm that the self-limiting growth of binary SPs is governed by a balance between electrostatic repulsion and van der Waals attraction.

Single-molecule chemical reaction reveals molecular reaction kinetics and dynamics.

Understanding the microscopic elementary process of chemical reactions, especially in condensed phase, is highly desirable for improvement of efficiencies in industrial chemical processes. Here we show an approach to gaining new insights into elementary reactions in condensed phase by combining quantum chemical calculations with a single-molecule analysis. Elementary chemical reactions in liquid-phase, revealed from quantum chemical calculations, are studied by tracking the fluorescence of single dye molecules undergoing a reversible redox process. Statistical analyses of single-molecule trajectories reveal molecular reaction kinetics and dynamics of elementary reactions. The reactivity dynamic fluctuations of single molecules are evidenced and probably arise from either or both of the low-frequency approach of the molecule to the internal surface of the SiO2 nanosphere or the molecule diffusion-induced memory effect. This new approach could be applied to other chemical reactions in liquid phase to gain more insight into their molecular reaction kinetics and the dynamics of elementary steps.

Theoretical study of resorufin reduction mechanism by NaBH4.

In the current work, the whole reduction mechanism of resorufin by sodium borohydride (NaBH4) has been investigated completely using quantum chemical theory for the first time. The possible pathways for each step were considered as much as possible. The calculated results reveal that the reduction mechanism for resorufin undergoes a nucleophilic addition with BH4(-), a synchronous proton abstraction from a carbon (C) atom, a protonation in a nitrogen (N) atom, and then a final hydrolysis process to obtain final reduced product dihydroresorufin. Interestingly, it was found that the protonation of N atom could induce a reduced product molecule with a Λ-type structure rather than a planar one, and the large alteration in geometry will induce different optical properties, such as fluorescent or nonfluorescent. More importantly, countercation Na(+) and solvation effect of H2O play important roles in reducing the activation energy in elementary steps, and their stabilization effect has been confirmed by NBO analysis. The detailed theoretical investigation for the reduction reaction of resorufin by NaBH4 will support some guidance for the similar reduction reaction for organic compounds like aldehydes and ketones.