A Single‐Atom Manipulation Approach for Synthesis of Atomically Mixed Nanoalloys as Efficient Catalysts

Synthesis of well‐defined atomically mixed alloy nanoparticles on desired substrates is an ultimate goal for their practical application. Herein we report a general approach for preparing atomically mixed AuPt, AuPd, PtPd, AuPtPd NAs(nanoalloys) through single‐atom level manipulation. By utilizing the ubiquitous tendency of aggregation of single atoms into nanoparticles at elevated temperatures, we have synthesized nanoalloys on a solid solvent with CeO₂ as a carrier and transition‐metal single atoms as an intermediate state. The supported nanoalloys/CeO₂ with ultra‐low noble metal content (containing 0.2 wt % Au and 0.2 wt % Pt) exhibit enhanced catalytic performance towards complete CO oxidation at room temperature and remarkable thermostability. This work provides a general strategy for facile and rapid synthesis of well‐defined atomically mixed nanoalloys that can be applied for a range of emerging techniques.     

One-phase supported titanium-based catalyst for polymerization of ethylene. IV. Effect of alkyl group at organoaluminium compound on catalyst performance

The effect of a basic layer (SiO₂—R₃Al intermediate) in the one-phase silica supported titanium-based catalyst was investigated using the simple model catalyst systems obtained by reacting the activated silica gel consecutively with R₃Al and TiCl₄. Mode of the interaction of SiO₂ with R₃Al—resulting in the formation of the basic layer—was observed via analysis of the concentration of the unreacted OH groups on the silica surface employing IR spectroscopy and via analysis of the concentration of aluminium in solvent using AA spectroscopy. It was found that nature of the alkyl group in R₃Al modified the structure of the basic layer, thus influencing the catalyst performance including the concentration of both the sum of Ti²⁺ and Ti³⁺ and the ESR-active Ti (III) centers. The sum of Ti²⁺ and Ti³⁺ ranged from 45 to 52 mol % and the amount of the ESR-active Ti (III) species ranged from 6 to 17 mol % of the all titanium content. A significant effect of alkyl group at organoaluminium compound on the molecular weight distribution of the resulting polymer was observed. © 1996 John Wiley & Sons, Inc.     

Preparation of styrene–divinyl benzene copolymer-supported platinum complexes and their catalytic properties in hydrosilylation

A new type of catalyst for the hydrosilylation of unsaturated monomers with dichloromethylsilane (DCMS) was prepared, which consisted of thiolmethylene-substituted styrene–divinyl benzene copolymer and platinum. When using DCMS as a hydrosilylation agent, these catalysts showed a high activity in the hydrosilylation of vinyl and acetylene monomers as styrene, alkyl vinyl silanes, acetylene, phenyl acetylene, butyl acrylate. The activities of catalysts were not significantly reduced even after 20 reuse cycles.     

正常金属-铁磁绝缘层-dx2-y2+idxy混合波超导结中的磁散射对隧道谱的影响

在正常金属铁磁绝缘层dx2-y2 idxy混合波超导隧道结中,考虑到铁磁绝缘层的磁散射和界面的粗糙散射效应,运用BogoliubovdeGennes(BdG)方程和BlonderTinkhamKlapwijk(BTK)理论,计算了隧道结中的准粒子传输系数和微分电导.研究表明:(1)磁散射和界面粗糙散射均可以压低电导峰,其中磁散射能使电导峰滑移,而粗糙界面散射却能阻止这种滑移,且两散射的共同作用可抑制由混合波两序参数的幅值比不同所导致的电导峰滑移;(2)随铁磁层离超导表面距离的增加,隧道谱在零偏压处由凹陷变成了零偏压电导峰,继而又演化为凹陷中的中心峰;(3)当铁磁层离开超导表面有若干相干长度时,隧道谱中将呈现一些子能级谐振峰.     

拟线性双曲组一类非局部混合初-边值问题的半整体C1解

在研究拟线性弦振动方程带第三类边值问题的精确边界能控性时,出现了拟线性双曲组一类非局部混合初-边值问题.论文先证明该类非局部混合问题局部C1解的存在惟一性,并考察其存在高度的性质,进而利用一致先验估计证明半整体C1解的存在惟一性,并以此为基础研究相应问题的精确边界能控性,最后为便于应用,将论文的结论写成了可化约方程组的情形.     

Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

Enhancing hydrogen evolution of MoS2 basal planes by combining single-boron catalyst and compressive strain

MoS₂ is a promising candidate for hydrogen evolution reaction (HER), while its active sites are mainly distributed on the edge sites rather than the basal plane sites. Herein, a strategy to overcome the inertness of the MoS₂ basal surface and achieve high HER activity by combining single-boron catalyst and compressive strain was reported through density functional theory (DFT) computations. The ab initio molecular dynamics (AIMD) simulation on B@MoS₂ suggests high thermodynamic and kinetic stability. We found that the rather strong adsorption of hydrogen by B@MoS₂ can be alleviated by stress engineering. The optimal stress of −7% can achieve a nearly zero value of ΔG_H (~ −0.084 eV), which is close to that of the ideal Pt–SACs for HER. The novel HER activity is attributed to (i) the B– doping brings the active site to the basal plane of MoS₂ and reduces the band-gap, thereby increasing the conductivity; (ii) the compressive stress regulates the number of charge transfer between (H)–(B)–(MoS₂), weakening the adsorption energy of hydrogen on B@MoS₂. Moreover, we constructed a SiN/B@MoS₂ heterojunction, which introduces an 8.6% compressive stress for B@MoS₂ and yields an ideal ΔGH. This work provides an effective means to achieve high intrinsic HER activity for MoS₂.     

Existence of Three Weak Solutions for a Class of Quasi-Linear Elliptic Operators with a Mixed Boundary Value Problem Containing $p(\cdot )$-Laplacian in a Variable Exponent Sobolev Space

In this paper, we consider a mixed boundary value problem to a class of nonlinear operators containing $p(\cdot )$-Laplacian. More precisely, we are concerned with the problem with the Dirichlet condition on a part of the boundary and the Steklov boundary condition on an another part of the boundary. We show the existence of at least three weak solutions under some hypotheses on given functions and the values of parameters.     

Growth of hexagonal quantum dots under preferential evaporation

We perform numerical simulations of hexagonal quantum dots of AlGaN semiconductors. We show that the competition between surface mass diffusion and evaporation rules the morphology of the quantum dots. The system displays three different behaviors: presence of separated islands without a wetting layer, islands dissolving into the wetting layer, or islands that do not evolve. The first behavior is of special interest because its optoelectrical properties are significantly improved in comparison with quantum dots with a wetting layer.