具有高稳定性以及光催化产氢活性的奇数环状异金属钛氧纳米团簇

利用太阳能是解决当前能源危机和环境问题的有效途径.二氧化钛是一种稳定性高、环境友好的新型光催化剂.近年来,具有精确结构信息的晶态钛氧团簇(PTCs)作为TiO₂的分子结构模型受到广泛关注.目前大多数PTCs含有烷氧基,在空气中易发生水解.这在很大程度上限制了对其光催化性能的研究.在无机钛氧簇的外围修饰大量的共轭有机配体是一种有效提升PTCs稳定性的方法.此外,异金属的嵌入有助于修饰微观电子结构,从而也将影响光催化性能.铝是地球上最丰富的金属元素,其水解产物也大量存在于地壳表面.因此,Ti和Al的水解和光催化研究引起了我们的兴趣.目前,只有少数几例低核的Al掺杂PTCs晶态材料被报道,且其制备过程都需要多步反应.因此,合成高核的包含Al的PTCs材料是一项有趣且充满挑战的工作.本文利用有机配体的保护和异金属离子的掺杂成功地提高了PTCs晶体材料的稳定性.通过研究Ti和Al离子的水解,制备了一例核-壳型的纳米轮簇[Al₇Ti₁₄(μ2-O)₇(μ3-O)₁₄(L)₃₅]·2CH₃CN(1;L=苯甲酸).该轮簇中包含罕见的奇数环状结构,是目前核数最高的包含Al的PTC.借助单晶X射线衍射可以清晰观察到无机{Al₇Ti₁₄}核与有机保护配体之间的配位模式.此外,利用红外光谱、热重和漫反射光谱对该化合物进行了进一步表征.有机配体层和Al³⁺占据了T_i⁴⁺周围的烷氧基位点,使得该化合物呈现较高的空气、热以及酸碱稳定性.在已报道的PTCs晶态材料中,该化合物也展现出较高的光催化产氢速率(402.88μmol g^-1h^-1).借助催化过程中的光致变色现象、电子顺磁共振谱、荧光光谱以及光电流响应,我们推测了该化合物催化水分解产氢机理.该项工作不仅为制备稳定的PTCs材料提供了基础,也为新型光催化剂的设计提供了新的思路.     

State-Independent Geometric Quantum Gates via Nonadiabatic and Noncyclic Evolution

Geometric phases are robust to local noises and the nonadiabatic ones can reduce the evolution time, thus nonadiabatic geometric gates have strong robustness and can approach high fidelity. However, the advantage of geometric phase has not been fully explored in previous investigations. Here,a scheme is proposed for universal quantum gates with pure nonadiabatic and noncyclic geometric phases from smooth evolution paths. In the scheme, only geometric phase can be accumulated in a fast way, and thus it not only fully utilizes the local noise resistant property of geometric phase but also reduces the difficulty in experimental realization. Numerical results show that the implemented geometric gates have stronger robustness than dynamical gates and the geometric scheme with cyclic path. Furthermore, it proposes to construct universal quantum gate on superconducting circuits, with the fidelities of single-qubit gate and nontrivial two-qubit gate can achieve 99.97% and 99.87%, respectively. Therefore, these high-fidelity quantum gates are promising for large-scale fault-tolerant quantum computation.     

金属-有机框架HKUST-1膜在气体分离中研究进展※

发展高效、绿色且节能的物质分离与纯化技术具有重要意义, 气体分离更是在工业、能源、医疗及科技等领域有着广泛的应用. 传统的聚合物膜在实现高效气体分离方面还面临许多挑战, 新型分离膜材料的开发是当前研究热点和难点. 金属-有机框架(Metal-Organic Frameworks, MOFs)材料作为一种新兴多孔配位聚合物, 由于其具有独特可设计的拓扑结构以及可调节的功能而受到科学家们的广泛关注. 为了克服粉体或块体MOFs很难被高效用于气体分离的难题, 开发可用于分离的MOFs膜材料是一项具有重要意义且具有挑战性的任务. HKUST-1作为一种代表性的MOFs材料, 由于其结构稳定且原料经济并具有多级孔径的结构, 常被用作制备成膜材料用于气体分离的研究和实际应用. 总结了近十年HKUST-1膜的制备方法及其气体分离性能的研究进展, 并对这个方向的研究提出了自己的看法和展望.     

NaY分子筛Lewis酸促进甲醇经亚硝酸甲酯分解制二甲氧基甲烷※

二甲氧基甲烷(Dimethoxymethane, DMM)作为一种基础有机化学品, 在树脂、溶剂、燃料等领域具有广泛用途. 传统合成方法采用甲醇甲醛缩合, 反应效率比较低. 亚硝酸甲酯(CH₃ONO)是一种性质活泼的气体, 可由甲醇、O₂、NO在无需催化剂的条件下获得, 其反应活性比甲醇高很多. 通过亚硝酸甲酯在常压条件下催化分解可以高效制备DMM. 本工作系统研究了不同类型分子筛的酸性对亚硝酸甲酯催化分解制备DMM的影响规律, 催化活性顺序为: NaY (97%)=HY (97%)>HZSM-5 (90%)>Hβ (89%)>NaZSM-5 (18%)>Naβ (6%), DMM选择性顺序为: NaY (53%)>HY (12%)=Naβ (12%)>NaZSM-5 (7%)>Hβ (4%)>HZSM-5 (3%), 其中NaY分子筛是一种性能优异的亚硝酸甲酯分解制备DMM的催化剂. 通过X射线衍射(XRD)、比表面及孔隙度分析(BET)、扫描电子显微镜(SEM)、吡啶红外(Py-FTIR)等结构表征手段, 发现分子筛的酸性位点是促进亚硝酸甲酯分解的活性中心, 而Na⁺和Al物种的Lewis酸是高选择性生成DMM的关键. 本工作可为DMM提供一种新的高效合成路线.     

Aggregation-induced emission luminogens and tunable multicolor polymer networks modulated by dynamic covalent chemistry

Aggregation-induced emission(AIE) based luminescent materials are generating intensive interest due to their unique fluorescence in the aggregation state. Herein we report a strategy of dynamic covalent chemistry(DCC) controlled AIE luminogens for the regulation of multicolor emission in reversible covalent polymer networks. Tetraphenylethene derived ring-chain tautomers were prepared, and the emission was readily controlled through multimode, such as changing the solvent, adding the base, and d...     

Dearomative spirocyclization via visible-light-induced reductive hydroarylation of non-activated arenes

A visible-light-induced spirocyclizative hydroarylation via reductive dearomatization of a series of non activated arenes including 2-phenyl indoles and naphthalene derivatives under mild conditions is de scribed. An intriguing chemoselective dearomative hydroarylation of 2-phenyl indoles is presented. Th dearomative hydroarylation protocol rapidly delivers valuable spirocycles with carbon-carbon doub bonds from readily accessible aromatic precursors in a single step.     

An experimental and numerical study of the localization behavior of tantalum and stainless steel

In general, the shear localization process involves initiation and growth. Initiation is expected to be a stochastic process in material space where anisotropy in the elastic–plastic behavior of single crystals and inter-crystalline interactions serve to form natural perturbations to the material’s local stability. A hat-shaped sample geometry was used to study shear localization growth. It is an axi-symmetric sample with an upper “hat” portion and a lower “brim” portion with the shear zone located between the hat and brim. The shear zone length is 870–890 μm with deformation imposed through a split-Hopkinson pressure bar system at maximum top-to-bottom velocity in the range of 8–25 m/s. We present experimental results of the deformation response of tantalum and 316L stainless steel samples. The tantalum samples did not form shear bands but the stainless steel sample formed a late stage shear band. We have also modeled these experiments using both conductive and adiabatic continuum models. An anisotropic elasto-viscoplastic constitutive model with damage evolution was used within the finite element code EPIC. A Mie-Gruneisen equation of state and the rate and temperature sensitive MTS flow stress model together with a Gurson flow surface were employed. The models performed well in predicting the experimental data. The numerical results for tantalum suggested a maximum equivalent strain rate on the order of 7 × 10⁴ s⁻¹ in the gage section for an imposed top surface displacement rate of 17.5 m/s. The models also suggested that for an initial temperature of 298 K a temperature in the neighborhood of 900 K was reached within the shear section. The numerical results for stainless steel suggest that melting temperature was reached throughout the shear band shortly after peak load. Due to sample geometry, the stress state in the shear zone was not pure shear; a significant normal stress relative to the shear zone basis line was developed.     

Discrete dislocation dynamics simulations to interpret plasticity size and surface effects in freestanding FCC thin films

Strong size effects have been experimentally observed when microstructural features approach the geometric dimensions of the sample. In this work experimental investigations and discrete dislocation analyses of plastic deformation in metallic thin films have been performed. Columnar grains representative of the film microstructure are here considered. Simulations are based on the assumptions that sources are scarcely available in geometrically confined systems and nucleation sites are mainly located at grain boundaries. Especially, we investigated the influence on the mesoscopic constitutive response of the two characteristic length scales, i.e., film thickness and grain size. The simulated plastic response qualitatively reproduces the experimentally observed size effects while the main deformation mechanisms appear to be in agreement with TEM analyses of tested samples. A new interpretation of size scale plasticity is here proposed based on the probability of activating grain boundary dislocation sources. Moreover, the key role of a parameter such as the grain aspect ratio is highlighted. Finally, the unloading behavior has been investigated and a strong size dependent Bauschinger effect has been found. An interpretation of these phenomena is proposed based on the analysis of the back stress distribution within the samples.     

岩石双孔爆破过程的流形元法模拟

在流形元基本理论基础上,引入断裂力学的裂纹产生及扩展判据,应用二阶流形元对岩石双孔爆破过程进行了研究,模拟了双孔同时起爆和毫秒延时起爆两种条件下裂纹的产生和扩展、块体的形成以及漏斗形成过程,分析了爆炸载荷作用下岩石的破坏规律以及起爆条件对该过程的影响,验证了流形元法在研究冲击载荷作用下岩石从连续体到不连续体破坏过程的准确性和有效性,为研究类似问题提供一个新的思路和方法。