电解水金属单原子催化剂的研究进展

氢能因其能量密度高、清洁无污染等特点,作为替代化石燃料的能源载体得到了广泛的研究.如何清洁高效地制备氢气受到了大量研究者的关注.当前,以化石能源的热反应所得副产氢气是主要来源.然而,采用该类方法不仅不能摆脱化石能源的使用以及温室气体的排放,还会造成生产氢气的纯度不高,碳氧化物杂质浓度过高的问题,严重影响氢气的后续使用.采用可再生能源(太阳能、风能等)所产富余电,进行电解水制氢,产生的氢气不含碳氧化合物杂质,纯度很高,可以真正实现碳的零排放,被认为是未来氢气来源的重要方式.目前,电解水制氢在制氢市场的所占份额较小,而造成这样局面的主要因素是该过程中的高能耗问题.为了降低能耗,开发高效催化剂加速两个电极上的电解反应的动力学尤为重要.近年,金属单原子催化剂(SACs)因其独特的结构,在很多研究中被用作电解水催化剂,进而开发出大量高性能的金属单原子电解水催化剂.本文综述了近年SACs在电解水催化方面的应用.首先,针对电解水反应本身,总结了阴阳极两侧的电极反应机制以及影响电极催化性能的关键吸附中间物种;然后,根据载体的不同,即合金、碳以及其它化合物将SACs分为三类,总结了相关电解水催化研究现状,并且针对不同类型SACs目前的发展情况,提出了它们各自存在的问题.其次,进一步总结了影响SACs电解水催化活性的因素,提出了四种决定SACs催化性能的影响因子,分别为金属原子的固有元素性质、配位环境、几何结构和负载量;同时讨论了这四类影响因素对SACs催化活性的影响机制,总结了调控各类影响因素的方法,为SACs的设计提出了一些建议.最后,展望了SACs在电解水催化中的应用,探讨了SACs在催化剂设计及催化机制研究方面的问题,提出了SACs在电解水催化中的未来发展方向.     

On Finite Element Approximations to a Shape Gradient Flow in Shape Optimization of Elliptic Problems

Shape gradient flows are widely used in numerical shape optimization algorithms. We investigate the accuracy and effectiveness of approximate shape gradients flows for shape optimization of elliptic problems. We present convergence analysis with a priori error estimates for finite element approximations of shape gradient flows associated with a distributed or boundary expression of Eulerian derivative. Numerical examples are presented to verify theory and show that using the volume expression is effective for shape optimization with Dirichlet and Neumann boundary conditions.     

A two-grid finite element method for the Allen-Cahn equation with the logarithmic potential

In this paper, we present a two-grid finite element method for the Allen-Cahn equation with the logarithmic potential. This method consists of two steps. In the first step, based on a fully implicit finite element method, the Allen-Cahn equation is solved on a coarse grid with mesh size H. In the second step, a linearized system whose nonlinear term is replaced by the value of the first step is solved on a fine grid with mesh size h. We give the energy stabilities of the traditional finite element method and the two-grid finite element method. The optimal convergence order of the two-grid finite element method in H¹ norm is achieved when the mesh sizes satisfy h = O(H²). Numerical examples are given to demonstrate the validity of the proposed scheme. The results show that the two-grid method can save the CPU time while keeping the same convergence rate.     

On mixed finite element approximations of shape gradients in shape optimization with the Navier–Stokes equation

For shape optimization of fluid flows governed by the Navier–Stokes equation, we investigate effectiveness of shape gradient algorithms by analyzing convergence and accuracy of mixed finite element approximations to both the distributed and boundary types of shape gradients. We present convergence analysis with a priori error estimates for the two approximate shape gradients. The theoretical analysis shows that the distributed formulation has superconvergence property. Numerical results with comparisons are presented to verify theory and show that the shape gradient algorithm based on the distributed formulation is highly effective and robust for shape optimization.     

A non-overlapping domain decomposition dual reciprocity method for solving the forward–backward heat equation in two-dimension

We apply a boundary element dual reciprocity method (DRBEM) to the numerical solution of the forward–backward heat equation in a two-dimensional case. The method is employed for the spatial variable via the fundamental solution of the Laplace equation and the Crank–Nicolson finite difference scheme is utilized to treat the time variable. The physical domain is divided into two non-overlapping subdomains resulting in two standard forward and backward parabolic equations. The subproblems are then treated by the underlying method assuming a virtual boundary in the interface and starting with an initial approximate solution on this boundary followed by updating the solution by an iterative procedure. In addition, we show that the time discrete scheme is unconditionally stable and convergent using the energy method. Furthermore, some computational aspects will be suggested to efficiently deal with the formulation of the proposed method. Finally, two forward–backward problems, for which the exact solution is available, will be numerically solved for two different domains to demonstrate the efficiency of the proposed approach.     

Heavy Alkali Metal Manganate Complexes: Synthesis,Structures and Solvent-Induced Dissociation Effects

Rare examples of heavier alkali metal manganates [{(AM)Mn(CH₂SiMe₃)(N^‘Ar)₂}_∞] (AM=K, Rb, or Cs) [N^‘Ar=N(SiMe₃)(Dipp), where Dipp=2,6-iPr₂-C₆H₃] have been synthesised with the Rb and Cs examples crystallographically characterised. These heaviest manganates crystallise as polymeric zig-zag chains propagated by AM⋅⋅⋅π-arene interactions. Key to their preparation is to avoid Lewis base donor solvents. In contrast, using multidentate nitrogen donors encourages ligand scrambling leading to redistribution of these bimetallic manganate compounds into their corresponding homometallic species as witnessed for the complete Li - Cs series. Adding to the few known crystallographically characterised unsolvated and solvated rubidium and caesium s-block metal amides, six new derivatives ([{AM(N^‘Ar)}_∞], [{AM(N^‘Ar)⋅TMEDA}_∞], and [{AM(N^‘Ar)⋅PMDETA}_∞] where AM=Rb or Cs) have been structurally authenticated. Utilising monodentate diethyl ether as a donor, it was also possible to isolate and crystallographically characterise sodium manganate [(Et₂O)₂Na(ⁿBu)Mn[(N^‘Ar)₂], a monomeric, dinuclear structure prevented from aggregating by two blocking ether ligands bound to sodium.     

含硫高折射率光学树脂合成及性能研究进展

作为无机玻璃的替代品,有机光学树脂具有轻质、抗冲击性好、易加工和可调性强等优点。折射率是光学树脂的主要参数之一,折射率的高低可直接影响成品镜片的厚度、美观性和舒适度。在不降低光学树脂综合性能的基础上提升光学树脂折射率一直是该领域的热点和难点,在光学树脂中引入高摩尔折射率的硫元素被认为是最有效和常用的方法之一。本文将含硫光学树脂分为烯烃类、环氧类、环硫类、多环类和聚氨酯类,简要综述了国内外近几年的研究进展,涉及单体合成、单体聚合以及单体结构对光学树脂综合性能影响,系统总结了以上材料的特性及发展。     

CoMn@NC催化5-羟甲基糠醛常压氧化为2, 5-呋喃二甲酸二甲酯

2, 5-呋喃二甲酸二甲酯(DMFDCA)这一生物质衍生的增值化学品是石油基聚合物单体对苯二甲酸(TPA)的理想替代品。本研究采用一步共热解法合成了两种廉价金属修饰的氮掺杂多孔碳催化剂CoMn@NC,并将其用于5-羟甲基糠醛(HMF)在温和条件下的需氧氧化。由Co₃Mn₂@NC-800催化HMF在50 ℃和常压氧气的条件下反应12 h后,得到产率为85%的DMFDCA。多孔催化剂的高比表面积提高了传质效率。Co纳米粒子(NPs)和呈原子级分散的Mn与掺杂在碳中的氮配位形成M―N_x。富含吡啶氮的碳基体中的缺电子金属位点有利于HMF和氧的活化。氧形成的超氧自由基阴离子的存在确保了半缩醛中间体和5-(羟基甲基)-2-糠酸甲酯(HMMF)的羟甲基的脱氢氧化,从而高选择性得到DMFDCA。该催化剂性能稳定,可适用于各种取代芳醇。该催化体系具有用于生产聚合物单体羧基酯的应用潜力。     

锰氧化物中氧空位的构建及其催化氧化苯系物作用机制研究进展

作为一种过渡金属氧化物,锰氧化物以其多晶型、储/释氧能力强、蕴含丰富氧物种、结构缺陷可控等优点被广泛应用于苯系物的热催化氧化。其中,具有众多特性的氧空位能有效促进苯系物的完全催化氧化,因而成为各界研究的焦点。我们综述了常见的氧空位构建方法及表征技术,并总结了在苯系物催化氧化过程中,锰氧化物中氧空位的几种重要作用机制对催化活性和抗水性能的积极影响。最后文章对氧空位构建新方法、形成机理、具体过程及其在锰氧化物热催化氧化苯系物领域中的应用进行了总结和展望。