Enhanced photoreactivity of MOFs by intercalating interlayer bands via simultaneous ?NCO and ?SCu modification

Herein, we propose a novel method to enhance the photoreactivity of an MOF catalyst by grafting isocyanate bonds ( NCO) and sulfhydryl-complexed copper ( SCu) onto ZIF-8 (NIF-SCu). The grafting process intercalated interlayer bands between the conduction and valence bands of ZIF-8, thereby providing a “ladder” for facile electron transition. The extreme improvement in the photoreactivity of NIF-SCu could be attributed to the enhancement in light responses in the range of 350–450 nm by  NCO groups and the widening of the visible light range of the MOF by  SCu groups. The formation of staggered energy levels in NIF-SCu could also narrow the band gap, lower the resistance, and facilitate the transfer of photogenerated carriers, thereby generating electrons with strong reduction potential in the  SCu conduction band. This study provides a new strategy for improving or even endowing the photoactivity of environmental functional materials with wide bandgaps.     

氮杂环卡宾-钯功能化的配位聚合物（NHC-Pd@Zn-L）：合成、表征及催化Suzuki-Miyaura交叉偶联反应

以\mathrm{1,3}-二(1-羧乙基)咪唑盐(HL)和Zn(NO₃)₂·6H₂O反应合成二维配位聚合物[Zn(L)₂] _n (Zn-L)，产物再与K₂PdCl₄在四氢呋喃溶液中反应引入氮杂环卡宾-钯（NHC-Pd）催化位点，制得催化剂NHC-Pd@Zn-L，并通过PXRD、TGA、ICP、SEM、EDS和XPS进行表征。结果表明，NHC-Pd@Zn-L具有良好的热稳定性且修饰后晶体的框架结构没有发生变化，Pd以NHC-Pd的形式结合在Zn-L中，并均匀分散在配位聚合物中。将NHC-Pd@Zn-L用于催化Suzuki-Miyaura交叉偶联反应，当以苯硼酸和溴苯为底物，催化剂用量为15 mg，乙醇为溶剂，碳酸钾为碱的条件下60℃反应6 h，产率达到>99%，而且催化剂易于回收并可循环使用3次。     

Dual functions of three-dimensional hierarchical architecture on improving the rate capability and cycle performance of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium-ion battery

The main obstacles in lithium-ion battery are limited by rate performance and the rapid capacity fading of LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811). Herein, a novel three-dimensional (3D) hierarchical coating material has been fabricated by in situ growing carbon nanotubes (CNTs) on the surfaces of Ni–Al double oxide (Ni–Al-LDO) sheets (named as LDO&CNT) with Ni–Al double hydroxide (Ni–Al-LDH) as both the substrate and catalyst precursor. The resultant LDO&CNT nanocomposites are uniformly coated on the surfaces of NCM811 by the physical mixing method. The rate capability of the resultant cathode material retains to 78.80% at a current rate of 3C. Its capacity retention increases by 6.7–14.42% compared with pristine NCM811 after 100 cycles within a potential range of 2.75–4.3 V at 0.5C. The improved rate capability and cycle performance of NCM811 are assigned to the synergistic effects between Ni–Al-LDO and CNTs. The hierarchical LDO&CNT nanocomposites coating on the surface of NCM811 avoids the aggregation of conductive CNTs and the stacking of Ni–Al-LDO nanosheets. Furthermore, it accelerates Li⁺ and electrons shuttle and reduces the reaction of Li₂O with H₂O and CO₂ in air, which results in Li₂CO₃ and LiOH alkali formation on the NCM811 surface.     

Electron transfer mediator PCN secreted by aerobic marine Pseudomonas aeruginosa accelerates microbiologically influenced corrosion of TC4 titanium alloy

Titanium alloys possess excellent corrosion resistance in marine environments,thus the possibility of their corrosion caused by marine microorganisms is neglected.In this work,microbiologically influenced corrosion (MIC) of TC4 titanium alloy caused by marine Pseudomonas aeruginosa was investigated through electrochemical and surface characterizations during a 14-day immersion test.Results revealed that the unstable surface caused by P.aeruginosa resulted in exposure of Ti2O3 and severe pitting corrosion with maximum pit depth of 5.7 μm after 14 days of incubation.Phenazine-1-carboxy[ate (PCN),secreted by P.aeruginosa,promoted extracellular electron transfer (EET) and accelerated corrosion.Deletion of the phzH gene,which codes for the enzyme that catalyzes PCN production,from the P.aeruginosa genome,resulted in significantly decreased rates of corrosion.These results demonstrate that TC4 titanium alloy is not immune to marine MIC,and EET contributes to the corrosion of TC4 titanium alloy caused by P.aeruginosa.     

Structural Cues for Understanding eEF1A2 Moonlighting

Spontaneous mutations in the EEF1A2 gene cause epilepsy and severe neurological disabilities in children. The crystal structure of eEF1A2 protein purified from rabbit skeletal muscle reveals a post-translationally modified dimer that provides information about the sites of interaction with numerous binding partners, including itself, and maps these mutations onto the dimer and tetramer interfaces. The spatial locations of the side chain carboxylates of Glu301 and Glu374, to which phosphatidylethanolamine is uniquely attached via an amide bond, define the anchoring points of eEF1A2 to cellular membranes and interorganellar membrane contact sites. Additional bioinformatic and molecular modeling results provide novel structural insight into the demonstrated binding of eEF1A2 to SH3 domains, the common MAPK docking groove, filamentous actin, and phosphatidylinositol-4 kinase IIIβ. In this new light, the role of eEF1A2 as an ancient, multifaceted, and articulated G protein at the crossroads of autophagy, oncogenesis and viral replication appears very distant from the “canonical” one of delivering aminoacyl-tRNAs to the ribosome that has dominated the scene and much of the thinking for many decades.     

Controlling thickness to tune performance of high-mobility transparent conducting films deposited from Ga-doped ZnO ceramic target

Structure modification has been found to tune significantly the transparent-conducting performance, especially mobility and conductivity of hydrogenated Ga-doped ZnO (HGZO) films. The strong correlation between film thickness and mobility of the films is revealed. The mobility increases quickly with increasing the thickness from 350 to 900 nm, and then tends to be saturated at further thicknesses. A higher mobility than 50 cm²/Vs can be achieved, which is an extra-high value for polycrystalline ZnO films deposited by using the sputtering technique. The thickness-dependent mobility originates from scatterings on grain boundaries and dislocation-induced defects controlled by thin-film growth. Based on the Volmer-Weber model, an expansion model is built up to describe the thickness-dependent crystal growth of the HGZO films, especially at the thick films. As a result, the 800 nm-thick HGZO film obtains the highest performance with high mobility of 51.5 cm²/Vs, low resistivity of 5.3 × 10^?4 Ωcm, and good transmittance of 83.3 %.     

ZnO Nanoplatelets with Controlled Thickness: Atomic Insight into Facet-Specific Bimodal Ligand Binding Using DNP NMR

Colloidal nanoplatelets (NPLs) and nanosheets with controlled thickness have recently emerged as an exciting new class of quantum-sized nanomaterials with substantially distinct optical properties compared to 0D quantum dots. Zn-based NPLs are an attractive heavy-metal-free alternative to the so far most widespread cadmium chalcogenide colloidal 2D semiconductor nanostructures, but their synthesis remains challenging to achieve. The authors describe herein, to the best of their knowledge, the first synthesis of highly stable ZnO NPLs with the atomically precise thickness, which for the smallest NPLs is 3.2 nm (corresponding to 12 ZnO layers). Furthermore, by means of dynamic nuclear polarization-enhanced solid-state ¹⁵N NMR, the original role of the benzamidine ligands in stabilizing the surface of these nanomaterials is revealed, which can bind to both the polar and non-polar ZnO facets, acting either as X- or L-type ligands, respectively. This bimodal stabilization allows obtaining hexagonal NPLs for which the surface energy of the facets is modulated by the presence of the ligands. Thus, in-depth study of the interactions at the organic–inorganic interfaces provides a deeper understanding of the ligand–surface interface and should facilitate the future chemistry of stable-by-design nano-objects.     

Surface modification mechanism of SiC particles using KH5X0 (X=5,6,7,8,9) silane coupling agents: First principle study

Silicon carbide surface modification is still a challenging task. Its modification mechanism is also still unclear. This paper provides a study of the surface modification mechanism of KH5X0 (X = 5, 6, 7, 8, 9) on the silicon carbide (111) using density functional theory. The electronic structures and densities of states of KH5X0 (X = 5, 6, 7, 8, 9) on SiC surfaces indicates that the surface modification mechanism is attributed to the electronic effects of the functional groups of KH5X0 (X = 5, 6, 7, 8, 9). From the results the easier it is for a functional group to obtain electrons, the better the modifying performance of silane coupling agent will be. Furthermore, the interface energy results showed that silicon carbide (111) modification performance by KH580 silane and KH590 silane is better than KH550, KH560, and KH570. The present work provides theoretical guidance for the fabrication of SiC heat sink products.     

Tribological behavior and applications of carbon fiber reinforced ceramic composites as high-performance frictional materials

Due to the favorable tribological, mechanical, chemical, and thermal properties, carbon fiber reinforced ceramic composites, especially carbon fiber reinforced carbon and silicon carbide dual matrix composites (C/C–SiC), has been considered as high-performance frictional materials. In this paper, current applications and recent progress on tribological behavior of C/C–SiC composites are reviewed. The factors affecting the friction and wear properties, including the content of silicon carbide and carbon matrix, carbon fiber preform architecture, as well as the matrix modification by alloy additives and C/C–SiC composites under various test conditions are reviewed. Furthermore, based on the current status of researches, prospect of several technically available solutions for low-cost manufacturing C/C–SiC composites is also proposed.