合成氨钌催化剂的晶体和形貌敏感性（英文）

哈伯-博施法合成氨反应是高温高压的耗能过程,因此降低该过程的能量消耗及开发温和条件下合成氨反应催化剂具有重要意义.金属钌是合成氨反应中最有前途的催化剂之一,一直备受广泛关注.确定金属钌催化剂的结构敏感性并提高其比质量活性是多相催化中亟待解决的重要问题.氮气(N_2)活化是合成氨反应中的关键步骤.本文通过第一性原理理论计算和微观动力学模拟方法系统研究了具有六方密排和面心立方晶体结构的钌催化剂上N_2活化过程和N_2解离反应速率.理论计算研究表明,在六方密排Ru形貌中,{2130}晶面具有最高的N_2解离活性,其次是{0001}台阶面,它们比六方密排Ru其他表面上N_2解离反应速率高3个数量级以上;在面心立方Ru形貌中,{211}和{311}表面上N_2解离活性最高.这些结果都表明台阶面/台阶位对氮气活化至关重要.虽然六方密排Ru {2130}晶面具有最低的N_2解离能垒,然而由于面心立方Ru上可以暴露更高密度的活性位点,使得面心立方Ru比六方密排Ru具有更高的N_2转化速率.本研究深入理解了N_2解离过程中,金属Ru催化剂形貌和晶相结构敏感性,这为设计和优化高活性的合成氨Ru催化剂提供了理论基础.     

不同晶相结构和形貌TiO2负载Ru催化剂的CO选择甲烷化

用水热法得到的钛酸纳米纤维前体,通过不同后处理方法合成了多种纳米结构的TiO₂．采用N₂等温吸附和BET比表面、X射线衍射、透射电镜和能量分散X射线分析表征了TiO₂及负载Ru催化剂的微结构,包括比表面、晶相结构和形貌以及Ru纳米颗粒尺寸分布等．对负载Ru催化剂在富氢条件下CO选择甲烷化反应活性测试表明：金红石相TiO₂和TiO₂-B为载体负载的Ru催化剂比锐钛矿相TiO₂负载的Ru催化剂表现出更高的反应性能．其活性区别说明了不同晶相结构和形貌TiO₂载体与Ru纳米颗粒的相互作用存在差异．     

振动和转动激发对N2在Fe(111)表面解离吸附的影响

N₂的解离化学吸附是工业合成氨的速控步骤. 基于最近构建的六维势能面,本文研究了N₂的初始振动激发和转动激发在Fe(111)表面的反应性的作用. 由于该反应具有重要的量子效应,通过六维量子动力学计算研究了入射能量低于1.6 eV 时振动激发的效应. 并采用准经典轨线计算揭示了高入射能量下的振动和转动激发的影响. 通过这些研究发现增加平动能量在一定程度上能提高解离几率,振动激发或转动激发能更有效地促进解离. 这项研究为重原子分子-表面反应的模式特异性动力学提供了有价值的见解.     

氮化钽团簇阴离子Ta3N3-解离吸附N2中的15N/14N同位素交换研究

氮气分子的吸附和活化是固氮研究中的重要过程. 近年来过渡金属氮化物由于在合成氨催化研究中的优异表现而受到广泛关注. 但是,氮化物物种与氮气分子在高温下反应的微观机制仍然不清楚,而该过程对于认识反应中的温度效应以及缩小气相团簇体系和凝聚相体系间的差距具有重要意义. 本文使用质谱观测到氮化钽团簇阴离子Ta₃¹⁴N₃^-和¹⁵N₂在高温下(393∽593 K)发生¹⁵N/¹⁴N同位素交换而产生¹⁴N₂/¹⁵N¹⁴N. 结合理论计算,阐述了同位素交换反应的微观机理以及升高温度对于N₂在Ta₃N₃^-上解离吸附的促进作用. 而在对比实验体系Ta₃¹⁴N₄^-/¹⁵N₂中,观察到升高温度只能加速¹⁵N₂在吸附产物Ta₃¹⁴N₄¹⁵N₂^-上的脱附. 这是由于氮空位是氮化物物种活化氮气的必要条件,而Ta₃N₄^-中由于不存在氮空位因此不能活化和解离氮气. 该研究为合成氨中氮化物物种中氮空位的作用提供了重要信息并且为固氮研究中高效催化剂的设计提供了线索.     

光沉积Ru和RuO2的锐钛矿TiO2纳米片的光解水产氧

采用水热法以HF作为结构调控剂合成了主要暴露（001）面的锐钛矿TiO₂纳米片,通过光沉积方法分别合成了负载Ru和RuO₂物种的光催化剂。利用X射线衍射、透射电镜和氢气程序升温还原等分析表征了催化剂的结构性质。通过光解水产氧反应来研究催化剂的催化性能,详细考察了Ru含量、负载方式以及氧化和还原处理等因素的影响,光解水产氧速率的差异证明了Ru物种在不同晶面的电荷-空穴分离效应。与负载单一助催化剂的Ru/TiO₂和RuO₂/TiO₂样品相比,活性最优的0.5%Ru-1.0%RuO₂/TiO₂样品由于负载了双助催化剂,其催化活性得到更大的提高,证实了在锐钛矿TiO₂上的晶面电荷-空穴分离效应.     

反夹心化合物[E-C{5-n}H{5-n}Nn-E]+和[E-C{5-n}H{5-n}Pn-E]+(n=1，2，3; E=Al，Ga，In，Tl)的理论研究

研究了含有低价族元素的反夹心化合物[E-C_{5-n}H_{5-n}N_n-E]⁺和[E-C_{5-n}H_{5-n}P_n-E]⁺(n=1,2,3; E=Al,Ga,In,Tl)．(η5, η5) 配位的反夹心构型[E-C_{5-n}H_{5-n}N_n-E]⁺ 在能量上不稳定或不存在．而(η5,η5)配位的反夹心构型[E-C_{5-n}H_{5-n}P_n-E]⁺不但在能量上稳定, 在解离过程中也具有稳定性． 对于含有相同的E元素来说,[E-C_{5-n}H_{5-n}P_n-E]⁺的解离稳定性随着n的增加而降低;而对于确定的n来说, 含有不同E的化合物的解离能是类似的．其中[E-C₄H₄P-E]⁺的解离稳定性与已知的[E-C₅H₅-E]⁺非常相似．C_{5-n}H_{5-n}P_n与E之间的相互作用主要是离子性的． 由于在(η5,η5)配位的[E-C_{5-n}H_{5-n}N_n-E]⁺中,E和P原子上都具有孤对电子,因此该反夹心化合物可以作为多电子供体．     

铂修饰的{001}面暴露的二氧化钛纳米片阵列的制备和光催化性能

采用有机溶剂热法在FTO衬底上制备{001}面暴露的单晶锐钛矿相TiO₂纳米片阵列,通过FESEM和XRD研究样品的形貌和晶体结构. 与水热法制备的纳米片阵列相比,有机溶剂热法制备的样品取向性更好. 采用光沉积方法在纳米片阵列上沉积Pt,所得到的Pt纳米颗粒粒径更为均匀,并且更容易沉积在{001}面上. 所负载的Pt 纳米颗粒增强了TiO₂纳米片的光吸收性能,同时大大减弱了光致发光强度. 在光催化性能测试中,具有最优负载量的样品催化性能提高了一倍. 与传统的Pt负载相比,{001}面的最优负载量显得相当小,这可能源于高活性{001}面的原子结构.     

高分辨的一氧化二氮光解离实验研究

利用"时间切片"离子速度成像技术研究了N₂O分子在134.20、135.20和136.43 nm波长下的真空紫外光解动力学. 实验中通过采集解离产物O(¹S_J=0)的离子影像来研究O(¹S_J=0)+N₂(X¹∑_g⁺)这一解离通道. 从各个波长下的实验影像可获得产物N₂(X¹∑_g⁺)的振动态分辨的结构,进而得到产物的总平动能谱和产物N₂的振动态布居. 实验结果表明在实验的光解波长下,产物N₂(X¹∑_g⁺)主要布居在v=2和v=3. 此外,还得到了产物N₂的振动态分辨的各向异性参数β,从中发现产物N₂的β值在三个解离波长下均表现出相似的特征,即随着振动量子数的增大,β值从趋近于2逐渐减小至1.4. 这一现象表明低振动态产物是通过一个以平行跃迁解离为主的解离过程产生的,而高振动态的产物来自于一个更加弯曲的中间构型的解离. 此推论与在平动能谱中所见到的最强转动态布居随着振动量子数的增大而出现的位移是相一致的.     

使用金属掺杂SnO2(110)作为表面催化剂的电催化CO2还原反应：通过调控Sn:O原子比例来控制产物

电催化CO₂还原反应可以产生HCOOH和CO,目前该反应是将可再生电力转化为化学能存储在燃料中的最有前景的方法之一. SnO₂作为将CO₂转换为HCOOH和CO的良好催化剂,其反应发生的晶面可以是不同的. 其中(110)面的SnO₂非常稳定,易于合成. 通过改变SnO₂(110)的Sn:O原子比例,得到了两种典型的SnO₂薄膜：完全氧化型(符合化学计量)和部分还原型. 本文研究了不同金属(Fe、Co、Ni、Cu、Ru、Rh、Pd、Ag、Os、Ir、Pt和Au)掺杂的SnO₂(110),发现在CO₂还原反应中这些材料的催化活性和选择性是不同的. 所有这些变化都可以通过调控(110)表面中Sn:O原子的比例来控制. 结果表明,化学计量型和部分还原型Cu/Ag掺杂的SnO₂(110)对CO₂还原反应具有不同的选择性. 具体而言,化学计量型的Cu/Ag掺杂的SnO₂(110)倾向于产生CO(g),而部分还原型的表面倾向于产生HCOOH(g). 此外,本文还考虑了CO₂还原的竞争析氢反应. 其中Ru、Rh、Pd、Os、Ir和Pt掺杂的SnO₂(110)催化剂对析氢反应具有较高的活性,其他催化剂对CO₂还原反应具有良好的催化作用.     

C3N4的高温高压同步辐射研究

利用激光加热金刚石对顶砧技术在高温高压条件下合成了纯beta相和立方相C₃N₄beta相C₃N₄所属对称群为P63/M (176).对石墨相与beta相C₃N₄的X射线衍射结果进行了精确分析, 得到优化晶胞参数.原位高压同步辐射X射线衍射分析表明, 在6GPa时由beta相到立方相C₃N₄的相转变已经发生, 之后两相共存直到19GPa时相变结束得到纯立方相C₃N₄.     

Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces

Polycrystalline copper electrocatalysts have been experimentally shown to be capable of reducing CO₂ into CH₄ and C₂H₄ with relatively high selectivity, and a mechanism has recently been proposed for this reduction on the fcc(211) surface of copper, which was assumed to be the most active facet. In the current work, we use computational methods to explore the effects of the nanostructure of the copper surface and compare the effects of the fcc(111), fcc(100) and fcc(211) facets of copper on the energetics of the electroreduction of CO₂. The calculations performed in this study generally show that the intermediates in CO₂ reduction are most stabilized by the (211) facet, followed by the (100) facet, with the (111) surface binding the adsorbates most weakly. This leads to the prediction that the (211) facet is the most active surface among the three in producing CH₄ from CO₂, as well as the by-products H₂ and CO. HCOOH production may be mildly enhanced on the more close-packed surfaces ((111) and (100)) as compared to the (211) facet, due to a change in mechanism from a carboxyl intermediate to a formate intermediate. The results are compared to published experimental data on these same surfaces; the predicted trends in voltage requirements are consistent between the experimental and computational data.     

Enhanced piezoelectric-induced catalysis of SrTiO3 nanocrystal with well-defined facets under ultrasonic vibration

Facet engineering of nanocomposite has been confirmed to be an efficient strategy to accelerate their catalytic performances, but to improve their piezoelectric catalytic activities by facet engineering has been seldom reported. Herein, we developed a series of SrTiO₃ nanocrystals with exposed {0 0 1} facet, dominant {1 1 0} facet and co-exposed {0 0 1} and {1 1 0} facets, respectively, and firstly revealed its piezoelectric catalytic performance under ultrasonic vibration. Moreover, the relationship between piezoelectric-induced catalytic activity and facet-dependence of SrTiO₃ nanocrystal was disclosed for the first time. The SrTiO₃ nanocrystal with co-exposed {0 0 1} and {1 1 0} facets exhibited effectively enhanced piezoelectric catalytic activity by degrading Rhodamine B (RhB) under ultrasonic vibration, as compared to that of SrTiO₃ nanocrystals with exposed {0 0 1} facet and dominant {1 1 0} facet, respectively. In addition, trapping experiments and active species quantitative experiments confirmed that the co-exposed {0 0 1} and {1 1 0} facets were beneficial to produce O₂⁻ and OH with the generation rates of 8.3 and 132.2 μmol g⁻¹ h⁻¹, respectively. The OH radical played a dominant role in piezoelectric catalytic process. Finally, the piezoelectric catalysis mechanism of SrTiO₃ surface heterojunction was proposed based on a DFT study. This study presents an in-depth understanding of piezoelectric-induced catalytic of perovskite nanocrystals with exposed well-defined facets.     

A density functional theory study of CH4 dehydrogenation on Co(1 1 1)

The dehydrogenation of CH₄ on the Co(1 1 1) surface is studied using density functional theory calculation (DFT). It is found that CH₄ is favored to dissociate to CH₃ and then transforms to CH₂ and CH by sequential dehydrogenation, and CH₄ activation into CH₃ and H is the rate-determining step on the Co(1 1 1) surface. CH₂ is quite unstable on Co(1 1 1) surface. CH dehydrogenation into C and H is difficult. CH₃ and H prefer to adsorb on 3-fold hollow hcp and fcc sites, and CH₂, CH and C prefer to adsorb on hcp sites.     

Facet‐Dependent Effect of Well‐Defined CeO2 Nanocrystals on the Adsorption and Dephosphorylation of Phosphorylated Molecules

CeO₂ nanocrystals (CN) with different morphologies (i.e., cube, octahedron, and rod) are prepared and the facet‐dependent effect of these CeO₂ nanocrystals on the adsorption and dephosphorylation of phosphorylated molecules is investigated for the first time using the model p‐nitrophenyl disodium orthophorphate (p‐NPP). Due to their different surface atomic configurations, the {111} and {110} facets have much higher adsorption capacity and kinetic catalytic activities than {100} facets. All the CeO₂ nanocrystals can intensely promote the dephosphorylation reaction owing to the strong interaction between Ce cations and phosphoryl oxygens resulting in the cleavage of phosphoester bonds. As was expected, the above facet‐dependent effect can be verified by the practical application results of the CeO₂ nanocrystals on the capture and dephosphorylation of phosphopeptides. Thus, surface engineering could be a useful and feasible strategy for not only fundamentally understanding the interaction between crystal facets and molecules but also effectively developing high‐performance functional materials.     

The initial oxidation of molybdenum: IV. Epitaxial growth of oxide on molybdenum

The oxide which grows in low oxygen pressure and at temperatures between 700 and 1000 K on molybdenum is shown to be MoO₂. The epitaxial relationships between the oxide and the metal (100), (110) and (111) surfaces are given. The epitaxial relationships of oxide on the molybdenum (100) and (110) surfaces are geometrically equivalent. The oxide grows on the (111) molybdenum surface with no major oxide plane parallel to the substrate. It is suggested that the epitaxy of MoO₂ on the (111) surface is a consequence of growth on {211} molybdenum facets. The atomic positions in the pairs of interfacial planes found are given. There is little agreement between the positions of ions in the oxide and substrate lattice sites. Only in the postulated case of MoO₂ on {211} Mo facets is a small misfit found.     

Thermal faceting of the rutile TiO2(001) surface

Temperature dependent faceting of rutile TiO₂ surfaces cut to the (001) plane has been reported [Tait and Kasowski, Phys. Rev. B20 (1979) 5178]. By comparing LEED data to beam positions calculated for various sets of facet planes, the facet planes have been identified. The first ordered structure observed on annealing ion bombarded surfaces is composed of {011} facets with the facet planes in a (2 × 1) reconstruction. The high temperature structure produced on annealing above 1300K is best described as {114} facets; however, there are deviations of the observed LEED pattern from that calculated for {114} facets, possibly because of the presence of related planes. LEED data have now been obtained on the behavior of (110), (100), (011), (114), and (001) surfaces in UHV. The observed stability of TiO₂ surfaces can be related to the Ti ion coordination numbers in the surface plane as derived from stoichiometric terminations of the rutile lattice.     

Ultrasound assisted deposition of highly stable self-assembled Bi2MoO6 nanoplates with selective crystal facet engineering as photoanode

The use of crystal facets of photocatalysts is well known as a promising strategy for the design of new photocatalysts with interesting physicochemical features for energy production applications. In this work, Bi₂MoO₆ thin films were synthesized by two methods, electrodeposition and sonoelectrodeposition. Preferential growth orientation depended on synthesis method. Results suggested that sonoelectrodeposition led to dominate the crystal facet {1 0 0} growth with self-assembled nanoplate morphologies while growth orientation in the {0 1 0} facet was dominant in electrodeposition in the absence of ultrasonic waves. As a highlight result, the {1 0 0} facet shows a smaller band gap, higher photocatalytic water splitting than the {0 1 0} facet. Efficient separation of charge pairs and long life time of photogenerated electrons was observed to be intrinsic features of the {1 0 0} facets. The higher charge transfer was confirmed by a higher photocurrent from linear sweep voltammetry and a smaller Nyquist radius arc. Ultrasound plays a key role in growth orientation and led to a production of homogeneous films with nanoplates which self-assembled together to form a flower-like structure. While in the absence of ultrasound the film has coral-like structure. Highly stable sonoelectrodeposited films exhibited incident photon-to-electron conversion efficiency (IPCE) of 22.4% at the specific wavelength of 500 nm. The sonoelectrodeposition method could act as a promising method for forming new films with specific crystal facet selection and developing as highly efficient photoanodes for PEC water splitting.     

Adsorption behavior and reaction properties of NO and CO on Rh(1 1 1)

Reactions between NO and CO on Rh(1 1 1) surfaces were investigated using infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. NO adsorbed on the fcc, atop, and hcp sites in that order, whereas CO adsorbed initially on the atop sites and then on the hollow (fcc + hcp) sites. The results of experiments with NO exposure on CO-preadsorbed Rh(1 1 1) surfaces indicated that the adsorption of NO on the hcp sites was inhibited by preadsorption of CO on the atop sites, and NO adsorption on the atop and fcc sites was inhibited by CO preadsorbed on each type of site, which indicates that NO and CO competitively adsorbed on Rh(1 1 1). From a Rh(1 1 1) surface with coadsorbed NO and CO, N₂ was produced from the dissociation of fcc-NO, and CO₂ was formed by the reaction of adsorbed CO with atomic oxygen from dissociated fcc-NO. The CO₂ production increased remarkably in the presence of hollow-CO. Coverage of fcc-NO and hollow-CO on Rh(1 1 1) depended on the composition ratio of the NO/CO gas mixture, and a gas mixture with NO/CO ? 1/2 was required for the co-existence of fcc-NO and hollow-CO at 273 K.     

Hydrogen adsorption,absorption and diffusion on and in transition metal surfaces: A DFT study

Periodic, self-consistent DFT-GGA(PW91) calculations are used to study the interaction of hydrogen with different facets of seventeen transition metals—the (100) and (111) facets of face-centered cubic (fcc) metals, the (0001) facet of hexagonal-close packed (hcp) metals, and the (100) and (110) facets of body-centered cubic (bcc) metals. Calculated geometries and binding energies for surface and subsurface hydrogen are reported and are, in general, in good agreement with both previous modeling studies and experimental data. There are significant differences between the binding on the close-packed and more open (100) facets of the same metal. Geometries of subsurface hydrogen on different facets of the same metal are generally similar; however, binding energies of hydrogen in the subsurface of the different facets studied showed significant variation. Formation of surface hydrogen is exothermic with respect to gas-phase H₂ on all metals studied with the exception of Ag and Au. For each metal studied, hydrogen in its preferred subsurface state is always less stable than its preferred surface state. The magnitude of the activation energy for hydrogen diffusion from the surface layer into the first subsurface layer is dominated by the difference in the thermodynamic stability of these two states. Diffusion from the first subsurface layer to one layer further into the bulk does not generally have a large thermodynamic barrier but still has a moderate kinetic barrier. Despite the proximity to the metal surface, the activation energy for hydrogen diffusion from the first to the second subsurface layer is generally similar to experimentally-determined activation energies for bulk diffusion found in the literature. There are also some significant differences in the activation energy for hydrogen diffusion into the bulk through different facets of the same metal.