Lattice Compression Revealed at the ≈1 nm Scale

Lattice tuning at the ≈1 nm scale is fascinating and challenging; for instance, lattice compression at such a minuscule scale has not been observed. The lattice compression might also bring about some unusual properties, which waits to be verified. Through ligand induction, we herein achieve the lattice compression in a ≈1 nm gold nanocluster for the first time, as detected by the single-crystal X-ray crystallography. In a freshly synthesized Au₅₂(CHT)₂₈ (CHT=S-c−C₆H₁₁) nanocluster, the lattice distance of the (110) facet is found to be compressed from 4.51 to 3.58 Å at the near end. However, the lattice distances of the (111) and (100) facets show no change in different positions. The lattice-compressed nanocluster exhibits superior electrocatalytic activity for the CO₂ reduction reaction (CO₂RR) compared to that exhibited by the same-sized Au₅₂(TBBT)₃₂ (TBBT=4-tert-butyl-benzenethiolate) nanocluster and larger Au nanocrystals without lattice variation, indicating that lattice tuning is an efficient method for tailoring the properties of metal nanoclusters. Further theoretical calculations explain the high CO₂RR performance of the lattice-compressed Au₅₂(CHT)₂₈ and provide a correlation between its structure and catalytic activity.     

Atomically Dispersed Iron Regulating Electronic Structure of Iron Atom Clusters for Electrocatalytic H2O2 Production and Biomass Upgrading

The integration of highly active single atoms (SAs) and atom clusters (ACs) into an electrocatalyst is critically important for high-efficiency two-electron oxygen reduction reaction (2e⁻ ORR) to hydrogen peroxide (H₂O₂). Here we report a tandem impregnation-pyrolysis-etching strategy to fabricate the oxygen-coordinated Fe SAs and ACs anchored on bacterial cellulose-derived carbon (BCC) (FeSAs/ACs-BCC). As the electrocatalyst, FeSAs/ACs-BCC exhibits superior electrocatalytic activity and selectivity toward 2e⁻ ORR, affording an onset potential of 0.78 V (vs. RHE) and a high H₂O₂ selectivity of 96.5 % in 0.1 M KOH. In a flow cell reactor, the FeSAs/ACs-BCC also achieves high-efficiency H₂O₂ production with a yield rate of 12.51±0.18 mol g_cat⁻¹ h⁻¹ and a faradaic efficiency of 89.4 %±1.3 % at 150 mA cm⁻². Additionally, the feasibility of coupling the produced H₂O₂ and electro-Fenton process for the valorization of ethylene glycol was explored in detail. The theoretical calculations uncover that the oxygen-coordinated Fe SAs effectively regulate the electronic structure of Fe ACs which are the 2e⁻ ORR active sites, resulting in the optimal binding strength of *OOH intermediate for high-efficiency H₂O₂ production.     

Morphological evolution and visible light-induced degradation of Rhodamine 6G by nanocrystalline bismuth tungstate prepared using a template-based approach

The cleaning of water contaminated with organic dyes is a crucial problem nowadays. The search for good catalysts is intense, and bismuth tungstates have attracted a lot of attention because of their catalytic properties which are related to their crystal structure and morphology. In this study, we show that Bi₂WO₆ (BWO) crystals synthesized by the surfactant-assisted hydrothermal method create a different morphology than non-assisted crystals. With the assistance of the PVP surfactant, even the BWO crystalline structure could change, crystallizing into a high-symmetry metastable phase. These changes in morphology imply a decrease in BWO catalytic activity, which shows that insightful control of BWO synthesis is necessary to improve the BWO properties.     

Fe-Co Alloyed Nanoparticles Catalyzing Efficient Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol in Water

Selective hydrogenation of C=O against the conjugated C=C in cinnamaldehyde (CAL) is indispensable to produce cinnamyl alcohol (COL). Nonetheless, it is challenged by the low selectivity and the need to use organic solvents. Herein, for the first time, we report the use of Fe-Co alloy nanoparticles (NPs) on N-doped carbon support as a selective hydrogenation catalyst to efficiently convert CAL to COL. The resultant catalyst with the optimized Fe/Co ratio of 0.5 can achieve an exceptional COL selectivity of 91.7 % at a CAL conversion of 95.1 % in pure water medium under mild reaction conditions, ranking it the best performed catalyst reported to date. The experimental results confirm that the COL selectivity and CAL conversion efficiency are, respectively promoted by the presence of Fe and Co, while the synergism of the alloyed Fe-Co is the key to concurrently achieve high COL selectivity and CAL conversion efficiency.     

Polymorphism in Bi2(SO4)3

A new polymorph of Bi₂(SO₄)₃ was prepared by reaction of LiBiO₂ with H₂SO₄ and its crystal structure was solved from X-ray powder diffraction. This new polymorph crystallizes in C2/c space group with lattice parameters a = 17.3383(3) Å, b = 6.77803(12) Å, c = 8.30978(13) Å, β = 101.4300(12)°. Bi₂(SO₄)₃ presents a layered structure made of SO₄ sulfate groups and signs of stereochemically active Bi³⁺ lone pairs. The new Bi₂(SO₄)₃ absorbs water to form Bi₂(H₂O)₂(SO₄)₂(OH)₂ through an intermediate Bi₂O(OH)₂SO₄ phase, and the transition is reversible when heated under vacuum.     

三维多孔花状ZnO微纳结构的合成及光催化性能

采用电沉积及后续的热处理技术,在Ti衬底上合成了一种三维多孔花状ZnO微纳结构薄膜. 这种ZnO结构是由包含大量纳米颗粒和孔洞的纳米薄片组成,纳米颗粒的大小可以通过调节电沉积时间和煅烧温度控制. 光催化性能的测试表明这种多孔ZnO薄膜是一种理想的光催化剂.     

Tunable structural color of anodic tantalum oxide films

Tantalum(Ta) oxide films with tunable structural color were fabricated easily using anodic oxidation.The structure,components,and surface valence states of the oxide films were investigated by using gazing incidence X-ray diffractometry,X-ray photoelectron microscopy,and surface analytical techniques.Their thickness and optical properties were studied by using spectroscopic ellipsometry and total reflectance spectrum.Color was accurately defined using L*a*b* scale.The thickness of compact Ta2O5 films was linearly dependent on anodizing voltage.The film color was tunable by adjusting the anodic voltage.The difference in color appearance resulted from the interference behavior between the interfaces of air-oxide and oxide-metal.     

Hydrothermal preparation of CuGaS2 crystallites with different morphologies

The CuGaS₂ crystallites with different morphologies were prepared at 160 °C through hydrothermal process by using CuCl, GaCl₃ solution, and thiourea as source materials. The samples were characterized by means of X-ray powder diffraction, element analysis, transmission electron microscopy, and photoluminescence (PL). In present route, as-prepared CuGaS₂ crystallites displayed spherical and whisker-like nanoparticles and snowflake-like micrometer particles. Room temperature PL spectrum of the snowflake-like crystallites exhibits a weak emission band at 540 nm and a broad strong emission band at 735 nm. The role that the reaction media played in the morphologies of the CuGaS₂ crystallites was investigated, and a possible reaction mechanism was proposed.     

Influence of the sulfur vacancies on the electronic properties of In16Sn4S32

High and low temperature forms of In₁₆Sn₄S₃₂ differ in color (black and orange-red, respectively) and lithium insertion properties. We have studied both forms by X-ray and neutron diffraction techniques and ¹¹⁹Sn Mössbauer spectroscopy. While diffraction techniques show no structural difference, Mössbauer spectra allow to differentiate both phases, as a consequence of the presence of Sn^II in the high-temperature form. We show from tight-binding calculations that both the differences in color and the tin oxidation states are related to the existence of sulfur vacancies in the local environment of the tin atoms.     

Silver porous nanotube built three-dimensional films with structural tunability based on the nanofiber template-plasma etching strategy

A facile and high-throughput strategy is presented to fabricate three-dimensional (3D) hierarchically porous Ag films, with clean surfaces, via plasma etching Ag-coated electrospun nanofiber template. The films are built of Ag porous nanotubes and are homogeneous in macro-size but rough and porous in nanoscale. Each nanotube-block is micro/nanostructured with evenly distributed nanopores on the tube walls. The film architecture (or the shape, arrangement, and distribution density of porous nanotubes; the number and size of nanopores) can be easily controlled by the nanofiber-template configuration, Ag coating, and plasma etching conditions. Such hierarchically porous films could be very useful, such as in catalysis, sensors, and nanodevices. They have exhibited significantly structurally enhanced surface-enhanced Raman scattering performance with good stability and reproduction, and shown the possibility of molecule-level detection. Also, the strategy is universal for fabricating other hierarchically structured 3D metal porous films, such as porous Ag hollow sphere arrays.