Topochemical Transformations of CaX2 (X=C,Si, Ge) to Form Free‐Standing Two‐Dimensional Materials

Topochemical transformations of layered materials CaX₂ (X=Si, Ge) are the method of choice for the high‐yield synthesis of pristine, defect‐free two‐dimensional systems silicane and germanane, which have advanced electronic properties. Based on solid‐state dispersion‐corrected calculations, mechanisms for such transformations are elucidated that provide an in‐depth understanding of phase transition in these layered materials. While formation of such layered materials is highly favorable for silicane and germanane, a barrier of 1.2 eV in the case of graphane precludes its synthesis from CaC₂ topochemically. The energy penalty required for distorting linear acetylene into a trans‐bent geometry accounts for this barrier. In contrast it is highly favorable in the heavier analogues, resulting in barrierless topochemical generation of silicane and germanane. Photochemical generation of the trans‐bent structure of acetylene in its first excited state (S₁) can directly generate graphane through a barrierless condensation. Unlike the buckled structure of silicene, the phase‐h of CaSi₂ with perfectly planar silicene layers exhibits the Dirac cones at the high symmetry points K and H. Interestingly, topochemical acidification of the cubic phase of calcium carbide is predicted to generate the previously elusive platonic hydrocarbon, tetrahedrane.     

Zn/Al层状双氢氧化物-聚氯乙烯纳米复合物的制备与性能

用共沉淀法制备油酸钾改性的Zn2+、Al 3+层状双氢氧化物(Zn/Al-LDH),以环己酮为溶剂,用溶液插层法制备了Zn/Al层状双氢氧化物-聚氯乙烯(PVC)纳米复合物。采用傅里叶红外(FT-IR)、X-射线衍射(XRD)、透射电镜(TEM)对复合材料的结构及形貌进行了表征,并用热分析仪、万能试验机和紫外分光光度计研究了复合物的热稳定性能、拉伸性能和紫外吸收性能。结果表明:Zn/Al-LDH纳米片层无序分散在PVC基体中;Zn/Al-LDH对PVC低温时的骨干脱氯化氢有促进作用;与PVC膜相比,复合膜的分解温度降低,高温碳化温度升高,复合膜的拉伸强度及断裂伸长率得到提高,在300~380nm具有一定的紫外吸收性能。     

Nickel‐Rich Layered Lithium Transition‐Metal Oxide for High‐Energy Lithium‐Ion Batteries

High energy‐density lithium‐ion batteries are in demand for portable electronic devices and electrical vehicles. Since the energy density of the batteries relies heavily on the cathode material used, major research efforts have been made to develop alternative cathode materials with a higher degree of lithium utilization and specific energy density. In particular, layered, Ni‐rich, lithium transition‐metal oxides can deliver higher capacity at lower cost than the conventional LiCoO₂. However, for these Ni‐rich compounds there are still several problems associated with their cycle life, thermal stability, and safety. Herein the performance enhancement of Ni‐rich cathode materials through structure tuning or interface engineering is summarized. The underlying mechanisms and remaining challenges will also be discussed.     

Co‐development of Crystalline and Mesoscopic Order in Mesostructured Zeolite Nanosheets

Mesoporous zeolites are a new and technologically important class of materials that exhibit improved diffusion and catalytic reaction properties compared to conventional zeolites with sub‐nanometer pore dimensions. During their syntheses, the transient developments of crystalline and mesoscopic order are closely coupled and challenging to control. Correlated solid‐state NMR, X‐ray, and electron microscopy analyses yield new molecular‐level insights on the interactions and distributions of complicated organic structure‐directing agents with respect to crystallizing zeolite frameworks. The analyses reveal the formation of an intermediate layered silicate phase, which subsequently transforms into zeolite nanosheets with uniform nano‐ and mesoscale porosities. Such materials result from coupled surfactant self‐assembly and inorganic crystallization processes, the interplay between which governs the onset and development of framework structural order on different length and time scales.     

Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism

The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe₂: [(PbSe)_1.14]₄[NbSe₂]₄, [(PbSe)_1.14]₃[NbSe₂]₃[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₃[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₂, [(PbSe)_1.14]₂[NbSe₂]₃[(PbSe)_1.14]₂[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance.     

Encapsulation of Functional Organic Compounds in Nanoglass for Optically Anisotropic Coatings

A novel approach is presented for the encapsulation of organic functional molecules between two sheets of 1 nm thin silicate layers, which like glass are transparent and chemically stable. An ordered heterostructure with organic interlayers strictly alternating with osmotically swelling sodium interlayers can be spontaneously delaminated into double stacks with the organic interlayers sandwiched between two silicate layers. The double stacks show high aspect ratios of >1000 (typical lateral extension 5000 nm, thickness 4.5 nm). This newly developed technique can be used to mask hydrophobic functional molecules and render them completely dispersible in water. The combination of the structural anisotropy of the silicate layers and a preferred orientation of molecules confined in the interlayer space allows polymer nanocomposite films to be cast with a well‐defined orientation of the encapsulated molecules, thus rendering the optical properties of the nanocoatings anisotropic.     

Utilization of Active Ni to Fabricate Pt–Ni Nanoframe/NiAl Layered Double Hydroxide Multifunctional Catalyst through In Situ Precipitation

Integration of different active sites into metallic catalysts, which may impart new properties and functionalities, is desirable yet challenging. Herein, a novel dealloying strategy is demonstrated to decorate nickel–aluminum layered double hydroxide (NiAl–LDH) onto a Pt–Ni alloy surface. The incorporation of chemical etching of Pt–Ni alloy and in situ precipitation of LDH are studied by joint experimental and theoretical efforts. The initial Ni‐rich Pt–Ni octahedra transform by interior erosion into Pt₃Ni nanoframes with enlarged surface areas. Furthermore, owing to the basic active sites of the decorated LDH together with the metallic sites of Pt₃Ni, the resulting Pt–Ni nanoframe/NiAl–LDH composites exhibit excellent catalytic activity and selectivity in the dehydrogenation of benzylamine and hydrogenation of furfural.     

Self‐Pillared,Single‐Unit‐Cell Sn‐MFI Zeolite Nanosheets and Their Use for Glucose and Lactose Isomerization

Single‐unit‐cell Sn‐MFI, with the detectable Sn uniformly distributed and exclusively located at framework sites, is reported for the first time. The direct, single‐step, synthesis is based on repetitive branching caused by rotational intergrowths of single‐unit‐cell lamellae. The self‐pillared, meso‐ and microporous zeolite is an active and selective catalyst for sugar isomerization. High yields for the conversion of glucose into fructose and lactose to lactulose are demonstrated.     

Synthesis of Carbon/Sulfur Nanolaminates by Electrochemical Extraction of Titanium from Ti2SC

Herein we electrochemically and selectively extract Ti from the MAX phase Ti₂SC to form carbon/sulfur (C/S) nanolaminates at room temperature. The products are composed of multi‐layers of C/S flakes, with predominantly amorphous and some graphene‐like structures. Covalent bonding between C and S is observed in the nanolaminates, which render the latter promising candidates as electrode materials for Li‐S batteries. We also show that it is possible to extract Ti from other MAX phases, such as Ti₃AlC₂ , Ti₃SnC₂ , and Ti₂GeC, suggesting that electrochemical etching can be a powerful method to selectively extract the “M” elements from the MAX phases, to produce “AX” layered structures, that cannot be made otherwise. The latter hold promise for a variety of applications, such as energy storage, catalysis, etc.     

Misfit‐Layered Bi1.85Sr2Co1.85O7.7−δ for the Hydrogen Evolution Reaction: Beyond van der Waals Heterostructures

Recent research on stable 2D nanomaterials has led to the discovery of new materials for energy‐conversion and energy‐storage applications. A class of layered heterostructures known as misfit‐layered chalcogenides consists of well‐defined atomic layers and has previously been applied as thermoelectric materials for use as high‐temperature thermoelectric batteries. The performance of such misfit‐layered chalcogenides in electrochemical applications, specifically the hydrogen evolution reaction, is currently unexplored. Herein, a misfit‐layered chalcogenide consisting of CoO₂ layers interleaved with an SrO–BiO–BiO–SrO rock‐salt block and having the formula Bi_1.85Sr₂Co_1.85O_7.7?δ is synthesized and examined for its structural and electrochemical properties. The hydrogen‐evolution performance of misfit‐layered Bi_1.85Sr₂Co_1.85O_7.7?δ, which has an overpotential of 589 mV and a Tafel slope of 51 mV per decade, demonstrates the promising potential of misfit‐layered chalcogenides as electrocatalysts instead of classical carbon.