射频等离子制备石墨烯负载Co3O4催化剂及其析氧性能研究

氢能的引入能有效提升配电网的供电可靠性,而电解水制氢是实现低碳转型的关键技术,开发高效的电解水催化剂势在必行。过渡金属氧化物储量大、催化活性高,是具有广阔应用前景的析氧反应催化剂。本文通过射频等离子体处理制备石墨烯上负载Co₃O₄析氧催化剂,XRD、Raman和XPS测试结果显示,二维结构石墨烯的引入加速表面电子迁移,增大了反应面积。等离子体处理促进了纳米粒子在石墨烯上的负载,利用等离子体刻蚀作用在催化剂表面制造出大量碳结构缺陷和氧空位结构,改善了活性位点分布,有效调控Co₃O₄电子结构,提高析氧催化活性。电化学测试表明,本文中合成的Co₃O₄@rGO在电流密度为50 mA·cm^-2时的过电位为410 mV,动力学反应速率较快,表现出优于商业IrO₂的析氧催化活性。     

高效Mo-Ni5P4双功能电催化剂的制备及其电解水性能研究

电催化制氢通过析氢反应(HER)和析氧反应(OER)同时产生氢气(H₂)和氧气(O₂),是一种高效且环境友好的产氢方式。但现阶段商业化的高效催化剂价格昂贵且储量较少，限制了电解水技术的大规模应用。因此，开发低成本、高稳定和环境友好的高效电催化剂，特别是基于非贵金属材料的磷化物电催化剂，成为近期研究热点。本研究通过水热和相对较低的磷化温度成功制备出了具有镂空纳米花结构的Mo掺杂Ni₅P₄催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对Mo-Ni₅P₄催化剂进行了表征，并研究了Mo-Ni₅P₄材料的电化学性能。研究发现，所合成的催化剂凭借掺杂对电子结构的改变，以及多孔纳米片的大表面积优势，提高了HER水解离步骤的速率。在碱性电解液中，Mo负载下的Ni₅P₄仅需116 mV的析氢过电位就可实现10 mA·cm^-2的电...     

温度对镍铁氧化物膜电极在碱液中析氧行为的影响

用直流磁控溅射设备制备的镍铁氧化物薄膜作为电解水的阳极材料在不同温度的1M KOH溶液中析氧活性不同。当电流密度为10mA/cm2时,过电位由22℃时的299mV下降到60℃时的292mV。在低过电位区,Tafel斜率b为27~28mV/dec;高过电位区,Tafel斜率为130~150mV/dec,并未发现斜率的突变。说明在一定范围内温度的提高并未改变析氧的速控步骤,同时该过程的动力学数据还表明电极析氧反应的可逆性没有显著变化。     

高价态W掺杂对NiFe磷化物全分解水制氢催化活性影响的研究

近年来，通过光伏辅助电催化(PV-EC)分解水制备“绿氢”成为实现碳中和目标的关键。然而，普通电解水催化剂不能满足PV-EC系统中较高的太阳能到氢能(STH)转换效率的需求。因此，获取价格低廉、低反应过电势的电催化剂材料极为重要。本文选取具有高价态的过渡金属W作为掺杂源，采用一步电沉积方法制备出NiFeW三元金属磷化物。通过一系列的表征发现，NiFeW磷化物电催化剂表现出优异的析氢反应(HER)和析氧反应(OER)活性，且作为双功能电催化剂时，在10 mA/cm²电流密度下W掺杂后样品的过电势降低了51 mV。使用NiFeW磷化物作为双功能电催化剂和太阳能电池(a-Si∶H/a-SiGe∶H/a-SiGe∶H)作为驱动源，PV-EC器件实现了超过7%的理论STH转换效率，对推动太阳能分解水制氢装置的实际应用具有重要意义。     

低铂Pt/SiC制备及对氧还原反应的催化性能表征

采用乙二醇回流法成功制备了理论含铂量为14;的Pt/SiC阴极催化剂.利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)对催化剂晶型结构、表面形貌和表面电子结构进行了表征.应用循环伏安法和旋转圆盘电极进行电化学测试,研究了Pt/SiC催化剂对氧还原反应催化活性.结果表明,在180℃条件下合成的Pt/SiC催化剂的平均粒径为3.4 nm,Pt是面心立方结构.Pt在SiC表面以0价为主,有利于O2在其表面的吸附和解离.Pt/SiC-180催化剂具有与商业Pt/C(20;)催化剂相近的氧还原催化性能.Pt/SiC-180催化剂的起始还原电位为0.95 V,氧还原过程以4-电子路径为主,且稳定性和抗甲醇中毒性能明显优于商业Pt/C催化剂.优良的催化性能和较低的含铂量使其有望成为低铂燃料电池阴极催化潜在材料.     

介孔Co3S4纳米棒的制备及电催化产氧性能的研究

以六水合硝酸钴(Co(NO3)2· 6H2O)为钴源,硫脲(CS(NH2)2)为硫源,采用溶剂热法和低温固相硫化的方法制备出了介孔Co3S4纳米棒.采用X射线衍射(XRD),扫描电镜(SEM)和透射电镜(TEM)等手段对于介孔Co3S4纳米棒进行表征,同时对介孔Co3S4纳米棒进行了电催化产氧性能测试.结果表明:介孔Co3S4纳米棒的起始过电位为0.37 V,塔菲尔斜率为76.95 mV/dec,具有高的电催化产氧性能.     

共沉淀法制备的Mn-Ce/TiO2催化剂低温脱硝性能研究

本文分别以NH4OH、(NH4)2CO3、NaOH作为沉淀剂,采用共沉淀法制备了一系列Mn-Ce/TiO2催化剂,并借助XRD、BET、NH3-TPD及XPS等测试手段对催化剂进行了表征,初步探讨了沉淀剂对Mn-Ce/TiO2催化剂SCR脱硝性能影响.结果表明:与(NH4)2CO3和NaOH相比,采用NH4OH作为沉淀剂制备的Mn-Ce/TiO2催化剂表现出了最佳的低温脱硝活性.当空速为16000 h-1,活性组分的负载量为15;时,催化剂在80℃的NO去除率达85;以上.这主要是由于该催化剂中的锰氧化物主要以无定形态存在;其孔结构更加细化、孔径较小及较大的孔容,为活性组分的均匀负载提供了有利条件;表面具有较多的弱酸性位点和中等酸性位点,且具有良好的氧化还原性强能力,有利于NO和NH3的吸附、氧化,有效的促进了催化剂的低温SCR脱硝活性.     

BiOCl/ZnO异质结型复合光催化剂的水热合成及其光催化性能

以醋酸锌、氯化钠、硝酸铋和氧氧化钠为原料,利用水热法合成了含BiOCl为1wt;、2wt;、4wt;、8wt;和16wt;的异质结型BiOCl/ZnO复合光催化剂.采用X射线粉末衍射(XRD)、扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、紫外可见漫反射光谱(UV-Vis DRS)和光致发光(PL)谱等系列手段对所制备的光催化剂进行了表征.以紫外光(254 nm)为光源,酸性橙Ⅱ为光催化反应降解模型,进行光催化活性测试,考察了复合BiOCl对ZnO光催化剂反应活性和稳定性的影响.研究表明,异质结型BiOCl/ZnO复合光催化剂的光催化性能明显优于纯ZnO.当复合BiOCl的含量为4wt;时,光催化活性最佳,为纯ZnO的3.4倍,同时该催化剂在循环使用中具有更好的稳定性.     

制备方法对铁钛催化剂物化性能及脱硝活性的影响

采用氨水共沉淀方法合成Fe3+/Fe2+摩尔比为1:1及掺一定量Ti4+的铁钛固溶体催化剂,与机械混合研磨方法制备的铁钛催化剂相比较.探讨不同制备工艺对催化剂物化性能及催化活性的影响.借助X射线衍射(XRD)、N2吸脱附、X射线光电子能谱(XPS)、程序升温还原(H2-TPR)、程序升温脱附(NH3-TPD)等手段对催化剂物理化学性质进行表征.结果表明:通过一步氨水共沉淀法及掺杂一定量Ti有利于提高催化剂的比表面积,抑制氧化物结晶及晶相转变,使得催化剂晶粒尺寸较小,提高低温催化活性;同时说明经过机械混合研磨制备的催化剂,只是氧化物晶体之间简单的机械混合,没有形成紧密的耦合作用,不能有效改善催化性能.     

Pt/Co-N-C电催化材料的制备及其碱性ORR性能

金属有机框架材料(MOFs)是一种制备过渡金属-氮-碳(M-N-C)氧还原电催化材料的有效前驱体，但在热解过程中结构坍塌等问题限制了其实际应用。本研究通过表面活性剂F-127包覆以及Zn掺杂对ZIF-67进行改性，并对改性后的Zn-ZIF-67@F-127在氩气气氛下进行热解，制得结构完整的Co-N-C载体。通过在Co-N-C载体表面进行Pt的负载，制备了Pt/Co-N-C复合氧还原反应(ORR)催化剂，并对其在碱性电解液中的ORR催化性能进行了探究。实验结果表明，F-127的加入提高了Zn-ZIF-67@F-127在热解过程中的形貌保持率，Pt/Co-N-C在O₂饱和的0.1 mol·L^-1 KOH中，催化剂的起始电位、半波电位、极限扩散电流密度分别为1.027 V、0.836 V和5.51 mA·cm^-2,与商用20%Pt/C性能相近。Pt与Co-N-C的协同作用使得催化剂不仅对ORR的四电子路径显示出高选择性，更在计时电流测试中表现出接近于商用20%Pt/C的稳定性与较商用20%Pt/C更优的抗甲醇性能。     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

Investigation of the Mechanism of Influence of Stress Corrosion on the Development of Macroplastic Instabilities of Aluminum–Magnesium Alloy

Crystallography Reports - Macroscopic jumps of plastic deformation (few percent in amplitude) on creep curves of aluminum–magnesium alloy, caused by a local effect of concentrated solution of...     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.     

A SAXS study of kinetics of aggregation of silica sols

SAXS in situ experiments on the evolution of TMOS solutions during hydrolysis and polycondensation lead to power laws with scaling exponents ≈ 2. It is suggested that this could be the result of the polydispersity of the samples and that only an apparent fractal dimension can be obtained in this way. Kinetic studies tend to indicate that agglomeration in the sol is the result of a diffusion-controlled process.     

Study of the possibility of interactive control of the surface profile of X-ray optical elements

We investigate the possibility of controlling the curvature parameters of parabolic mirrors that are modular elements of two types consisting of a base and thin inserts placed at the opposite side of the work surface. In the first type of modular elements, bending is controlled by the difference in the coefficients of the thermal expansion of the base and inserts. In the second type of elements, the profile is changed by the piezoelectric straining of the inserts under an electric field. A correlation is established between the parameters of modular elements and their surface curvature profile.