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。     

Recent Developments and Practical Feasibility of Polymer‐Based Antifouling Coatings

While nature has optimized its antifouling strategies over millions of years, synthetic antifouling coatings have not yet reached technological maturity. For an antifouling coating to become technically feasible, it should fulfill many requirements: high effectiveness, long‐term stability, durability, ecofriendliness, large‐scale applicability, and more. It is therefore not surprising that the search for the perfect antifouling coating has been going on for decades. With the discovery of metal‐based antifouling paints in the 1970s, fouling was thought to be a problem of the past, yet its untargeted toxicity led to serious ecological concern, and its use became prohibited. As a response, research shifted focus toward a biocompatible alternative: polymer‐based antifouling coatings. This has resulted in numerous advanced and innovative antifouling strategies, including fouling‐resistant, fouling‐release, and fouling‐degrading coatings. Here, these novel and exciting discoveries are highlighted while simultaneously assessing their antifouling performance and practical feasibility.     

Hetero-assembly of colloidal particles in concentrated non-aqueous suspensions by polymer dispersant design

Although many colloidal assembling systems have been reported, most systems suffer from severe aggregation under high solid concentrations, which can often be observed in typical hetero-aggregation system. In this study, we created a hetero-assembly system using concentrated (~50 vol%) suspensions by mixing large SiO₂ particles modified with polyacrylic acid partially complexed with oleylamine (PAA-OAm) and small SiO₂ particles modified with polyethyleneimine partially complexed with oleic acid (PEI-OA) in a non-aqueous solvent. We demonstrated that hetero-assembly is driven by the interactions between the uncomplexed carboxyl/amine groups of the PAA/PEI present on the particles, while severe aggregation is simultaneously prevented by the steric repulsions of the aliphatic oleyl chains. Comparison of the cross sections of the in-situ solidified hetero-assembled suspensions with those of ideally assembled structures which were reproduced by a simulation considering the statistical distribution of particles strongly supported successful particle assembling via the proposed approach. The results revealed that the OA content in the PEI-OA complex was the dominant factor that controlled the dispersion and assembling state of the binary particles. The significance of this study is that our findings will provide a class of colloidal dispersion state which binary particles were assembled in a high solid content suspension without forming strong aggregates.     

Synergistic reinforcement of surface modification on improving the bonding of veneering ceramics to zirconia

Veneering ceramics should be strongly bonded to zirconia core in order to achieve successfully long-term clinical practice. Indeed, to pursue the high zirconia core–veneering ceramic bonding is still a concerned issue. In this regard, this study was to treat zirconia surface using a 3?wt% Si₃N₄ solution in 4?M NaOH and to investigate the effect of soaking time (5, 10, and 20 days) on the surface properties of zirconia and shear bond strength between zirconia and veneering ceramics. The residual veneering ceramics on zirconia surfaces and failure modes were also examined after fracture. The results showed that the phase composition of zirconia before and after surface modification was not changed. The elemental mapping and depth profiling consistently revealed the soaking-time-dependent Si content on the zirconia surface. The surface roughness of zirconia was significantly (P?<?0.05) increased with the increasing soaking time. When zirconia was treated for 10 days, the shear bond strength value of 27.4?MPa was significantly (P?<?0.05) higher than the control (18.6?MPa), associated with greater remaining amounts of veneering ceramics on the zirconia surface. The failure mode of the treated zirconia was almost the mixed failure. On the basis of the data, surface modification using Si₃N₄ in NaOH solution for zirconia core could be a simple and effective method for enhancing the veneering ceramic–zirconia bonding.     

AlF3-modified LiCoPO4 for an advanced cathode towards high energy lithium-ion battery

Surface-interface reaction between the electrode and electrolyte plays a key role in lithium-ion storage properties, especially for high voltage cathode such as LiCoPO₄ and Ni-riched cathode. Generally, surface modification is an effective method to improve the electrochemical performance of electrode materials. Herein, in order to revise the LiCoPO₄ cathode with desirable properties, uniform AlF₃-modified LiCoPO₄ (LiCoPO₄@AlF₃) cathode materials in nano-sized distribution are synthesized. XRD result indicates that there is no structural transformation observed after AlF₃ coating. TEM characterization and XPS analysis reveal that the surface of LiCoPO₄ particle is coated by a nano-sized uniform AlF₃ layer. Further, the electrochemical results indicate that AlF₃ layer significantly improves the cycling and rate performances of LiCoPO₄ cathode within the voltage range of 3.0–5.0 V. After a series of optimization, 4 mol% AlF₃-coated LiCoPO₄ material exhibits the best properties including an initial discharge capacity of 159 mA h g^?1 at 0.1 C with 91% capacity retention after 50 cycles, especially a discharge capacity of 90 mA h g^?1 can be obtained at 1 C rate. CV curves indicate that the polarization of cathode is reduced by AlF₃ layer and EIS curves reveal that AlF₃ layer relieves the increase of resistance to facilitate Li-ion transfer at the interface between electrode and electrolyte during the cycling process. The enhanced electrochemical performances are attributed to that the AlF₃ layer can stabilize the interface between the cathode and electrolyte, form steady SEI film and suppress the electrolyte continuous decomposition at 5 V high voltages. This feasible strategy and novel characteristics of LiCoPO₄@AlF₃ could promise the prospective applications in the stat-art of special lithium-ion battery with high energy and/or power density.     

Novel Flower-Like ZnO Hybridized with Acrylic Ester Resin for Enhanced Oil Absorption Properties

The acrylic ester resins have potential applications in for treatment of oily wastewater due to their high oil retention capacity and excellent cycle performance. Herein, a novel acrylic ester hybrid resins composed by poly(n-butylacrylate-co-styrene) resins and flower-like ZnO clusters were prepared using a combination of hydrothermal and suspension polymerization. The hybrid resins can remove a broad variety of oils from water with the maximum oil absorption performance of 30.87?g/g. More importantly, the hybrid resins are reversible and maintain high oil absorption properties after oils absorption-regeneration, making them promising candidates for treatment of oily wastewater.     

Research on hydrophobicity of electrospun Fe3O4/PVDF nanofiber membranes under different preparation conditions

Abstract

Preparation condition can affect the structure and the properties of nanofiber membrane. In order to explore suitable conditions to prepare the Fe₃O₄/PVDF nanofiber membrane with good hydrophobicity, the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes obtained by electrospinning was investigated by changing preparation conditions like weight percentage of Fe₃O₄ nanoparticles, blending quality concentration of poly (vinylidene fluoride) (PVDF) and Fe₃O₄ nanoparticles, and positive voltage. And the variations of hydrophobicity of Fe₃O₄/PVDF nanofiber membranes modified by 1H, 1H, 2H, 2H-perfluorodecyl trimethoxysilane were studied. The results show that the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes has changed under different preparation conditions. The contact angles of samples increased after a modification by 1H, 1H, 2H, 2H-perfluorodecyl trimethoxysilane, which indicates that the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes has been enhanced.     

氟化铵对纳米金红石型钛硅复合氧化物表面改性研究

以硫酸氧钛为钛源、硅酸钠为硅源,采用改进的水解沉淀法制备了纳米金红石型钛硅复合氧化物(TiO_2-SiO_2),以氟化铵(NH_4F)为表面改性剂,采用水热法在不同溶剂中对TiO_2-SiO_2进行改性,并通过X-射线衍射仪、傅里叶红外光谱仪、扫描电镜、原子力显微镜和接触角测量仪等,研究了不同溶剂对改性效果的影响。结果表明,以异丙醇为溶剂进行NH_4F改性时,由于表面Si-F键的形成、异丙醇表面自组装和表面微纳分层粗糙结构的形成等因素的协同作用,改性后的纳米金红石型TiO_2-SiO_2比表面积大,具有良好的表面性能,其比表面积达332 m2/g,水和二碘甲烷接触角分别达到147.1°和147.2°。     

Reversible data hiding based on RSBEMD coding and adaptive multi-segment left and right histogram shifting

By leveraging the secret data coding using the remainder storage based exploiting modification direction (RSBEMD), and the pixel change operation recording based on multi-segment left and right histogram shifting, a novel reversible data hiding (RHD) scheme is proposed in this paper. The secret data are first encoded by some specific pixel change operations to the pixels in groups. After that, multi-segment left and right histogram shifting based on threshold manipulation is implemented for recording the pixel change operations. Furthermore, a multiple embedding policy based on chess board prediction (CBP) and threshold manipulation is put forward, and the threshold can be adjusted to achieve adaptive data hiding. Experimental results and analysis show that it is reversible and can achieve good performance in capacity and imperceptibility compared with the existing methods.     

碳脱氧在钢包顶渣改质中的应用

 为了进一步降低夹杂物缺陷并提高产品质量,基于碳脱氧进行了钢包顶渣改质的研究。冷轧产品的生产工艺为铁水预处理→转炉→RH精炼→连铸,为减少钢中夹杂物质量分数,需要进行钢包顶渣改质,同时降低钢包顶渣TFe质量分数。采用粒碳部分替代铝渣球的方法进行基于碳脱氧工艺的钢包顶渣改质,试验结果表明,顶渣改质效果良好,在顶渣TFe质量分数、中间包钢水游离氧明显降低的同时铸坯中Al₂O₃夹杂物得到优化;“30 kg粒渣+铝渣球”工艺降低生产成本5.16元/t(钢)。