COORDINATION POLYMERIZATION OF BENZOTRIAZOLE ON THE SURFACE OF METALLIC COPPER

The coordination polymerization of benzotriazole with metallic copper has been investigated by infrared and X-ray photoelectron spectroscopies. We found that benzotriazole could react with copper (0) under mild conditions to form bis (benzotriazolato) copper (Ⅱ) and benzotriazolato copper (Ⅰ)which covered the surface of copper metal in the shape of polymeric materials. Since benzotriazole is of great interest as a ligand in that its presence in many biological system with metal ions, and is considered as a corrosion inhibitor, this work will be in favour of the study of protective corrosion.

CAD-DIRECTED INSPECTION PLANNING FOR FREEFORM SURFACE USING CONTACT PROBES

A methodology for CAD-directed measurement of freeform surface using a coordinate measuring machine equipped with a touch-trigger probe is presented, mainly including adaptive sampling of measurement points and registration of freeform surface. The proposed sampling method follows four steps： Freeform surface is fitted by bi-cubic B-spline; Curvedness measure of the surface is computed; Given a number of sampling points, an iterative algorithm is constructed for selecting a set of measurement points by employing the curvedness information; The measurement points is regularized for tradeoff between maximizing the measurement accuracy and minimizing the sampling time and cost. The aforesaid algorithm is demonstrated in term of a marine propeller blade. An offset surface registration method is presented to improve alignment accuracy of freeform objects, and Monte Carlo simulation is conducted to verify the effectiveness of the method.

Phytate-Coordination Triggered Enrichment of Surface NiOOH Species on Nickel Foam for Efficient Urea Electrooxidation

Nickel(Ni)-based materials are promising electrocatalysts for the urea electrooxidation reaction, as the in situ formed NiOOH species on their surface during operation are catalytically active sites. In this work, phytate-coordinated Ni foam(PA-NF)is shown to deliver a high catalytic performance, with a potential as low as 1.38 V at 10m A/cm2, a Tafel slope as low as 64.1 mV/dec, and superior catalytic stability. Characterizations revealed that such a high performance was ascribed to the kinetic acceleration of surface reconstruction and the enriched NiOOH active species on the PA-NF surface owing to PA-coordination induced upshift of d-band center of Ni sites.Overall, a novel and simple strategy is provided for designing the efficient as well as universal Ni-based catalyst for the electrooxidation of urea, which can also be extended to other transition-metal-based systems.

Exploring electronic-level principles how size reduction enhances nanomaterial surface reactivity through experimental probing and mathematical modeling

Size reduction can generally enhance the surface reactivity of inorganic nanomaterials.The origin of this nano-effect has been ascribed to ultrasmall size,large specific surface area,or abundant defects,but the most intrinsic electronic-level principles are still not fully understood yet.By combining experimental explorations and mathematical modeling,herein we propose an electronic-level model to reveal the physicochemical nature of size-dependent nanomaterial surface reactivity.Experimentally,we reveal that competitive redistribution of surface atomic orbitals from extended energy band states into localized surface chemical bonds is the critical electronic process of surface chemical interactions,using H_(2)O_(2)-TiO_(2)chemisorption as a model reaction.Theoretically,we define a concept,orbital potential(G),to describe the electronic feature determining the tendency of orbital redistribution,and deduce a mathematical model to reveal how size modulates surface reactivity.We expose the dual roles of size reduction in enhancing nanomaterial surface reactivity-inversely correlating to orbital potential and amplifying the effects of other structural factors on surface reactivity.

Surface Coordination Decouples Hydrogenation Catalysis on Supported Metal Catalysts

Supported metal catalysts integrating advantages of catalytic hydrogenation and stoichiometric reduction are highly desirable for the green production of fine chemicals.Decoupling catalytic hydrogenation into H_(2)activation and selective reduction taking place at different locations is expected to provide an effective strategy to fabricate such catalyst systems.Herein,we report a decoupled hydrogenation system by modifying Pt catalysts supported on reducible In2O3 with ethylenediamine(EDA).The system exhibits good catalytic performance in oximes production from nitroalkanes,an industrially important reaction,by employing H_(2).Systematic studies demonstrate that the surface coordination of EDA on Pt is crucial to passivate the Pt surface from nitro hydrogenation without inhibiting H_(2)activation.The activated H_(2)species can then transfer and reduce the In_(2)O_(3)support in situ to generate sustainable stoichiometric reducing agents for the chemoselective reduction of nitroalkanes.Based upon the mechanistic understanding,a sustainable strategy for the production of oximes has been successfully fabricated.

Surface Organometallic Chemistry for Single-site Catalysis and Single-atom Catalysis

Although driven by different research interests,single-site catalysts and single-atom catalysts are both believed to be model systems bridging homogeneous and heterogeneous catalysis.The two concepts are similar but different.In this review,we will first explain the difference between single-atom catalysis and single-site catalysis,in terms of their goals,synthetic methods and coordination structures of corresponding catalysts.Then,we will introduce the surface organometallic chemistry method,a method traditionally used for synthesizing single-site catalyst.We will explain why it might benefit the single-atom catalysis community.At last,the choice of support to accommodate the method for synthesizing single-atom catalysts will be discussed.