Herein, we describe a versatile synthetic strategy for constructing Prussian Blue (PB)-coated polymeric nanocapsules (PB@nanocapsules) with tunable sizes and controlled PB loading. A soft template was first formed from a miniemulsion composed of water/chloroform/hexadecane (94.55:5:0.2, w/w/w), using P4VP82-b-PDMAA180 as a stabilizer and varying amounts of P4VP homopolymer as a hydrophobe and additional reactive site provider. Crosslinked nanocapsules were obtained by adding 1,2-bis-(2-iodoethoxy)ethane (BIEE) as a crosslinker. The resulting nanocapsules exhibited average hydrodynamic diameters ranging from approximately 282 nm (without P4VP homopolymer) down to 58 nm (with 0.01 g P4VP homopolymer), as determined by DLS and TEM. Subsequently, sequential coordination with sodium pentacyanoammine -ferroate(II) hydrate (Na3 [Fe(CN)5NH3]), followed by the addition of FeCl3, yielded a uniform PB coating, as confirmed by the appearance of a characteristic absorption peak at 780 nm in the UV–Vis spectra and a CN stretching shift from 2060 to 2070 cm−1 in FT-IR. TEM and HAADF-STEM with EDX mapping revealed the homogeneous distribution of Fe across the nanocapsule shells. The PB loading could be further controlled by varying the Fe3+ addition (5.0 × 10−3–4.5 × 10−2 mmol), with higher loading improving thermal stability. This rational design provides a robust and generalizable platform for engineering polymer–inorganic hybrid nanostructures with tailored functionalities.

Various nickel-based catalyst-doped silver nanomaterials ([Ni]@Ag) were synthesized by chemical reduction in an aqueous phase. The surface topography and composition of the catalyst were verified using field-emission scanning electron microscopy (FE-SEM) and energy-dispersive X-ray spectroscopy (EDX). In the electrocarboxylation of allyl chloride with CO2, [Ni]@Ag served as the catalytic cathode, whereas Mg functioned as the sacrificial anode. Under normal CO2 pressure at 0 degrees C, the yield of vinylacetic acid reached 95%. Notably, [Ni]@Ag demonstrated high reusability for CO2 allylation, with no loss in catalytic efficiency. A preliminary reaction mechanism was also proposed.

Developing bifunctional oxygen electrocatalysts based on non-precious elements for the air electrodes of rechargeable Zn-air batteries (ZABs) remains a significant challenge. Herein, by adjusting th Co precursor content, we synthesized a bifunctional electrocatalyst (CoFe@NC-5) comprising CoFe/Co nanoalloys (∼16 nm) encapsulated in N-doped carbon. The CoFe@NC-5 catalyst features the highest metal loading (37.24 wt% Co + Fe), uniform nanoalloy distribution, a unique encapsulated structure, and well-defined heterojunction interfaces between CoFe and Co phases. These characteristics endow CoFe@NC-5 with excellent bifunctional oxygen electrode activity, as evidenced by a low potential gap (ΔE) of 0.757 V between the half-wave potential for the oxygen reduction reaction (ORR, 0.84 V) and the potential for the oxygen evolution reaction (OER, 1.597 V) at 10 mA cm-2. Density functional theory (DFT) calculations further reveal that the heterojunction interfaces in the CoFe/Co heterostructure of the CoFe@NC-5 catalyst significantly enhance interfacial electron accumulation and shift the d-band center closer to the Fermi level, thereby boosting its ORR and OER activities. Furthermore, a rechargeable ZAB assembled with CoFe@NC-5 as the air electrode exhibits a high power density of 363.7 mW cm-2, a specific capacity of 785.8 mA h gZn-1 at 50 mA cm-2, and stable charge-discharge cycling for 330 hours.

Heavy metal ions pose a significant threat to the environment and human health. Developing a highly sensitive heavy metal ion detection method is desirable. In this study, the Au(I)-catenates were formed in glucoamylase (Glu) and neomycin sulfate (Ne). The polychrome metal nanoparticles (MNPs) were prepared based on the template of Au(I)-catenates. The simple and ultrasensitive visual sensor array for the determination of heavy metal ions was established based on the color information extracted from polychrome MNPs. The addition of heavy metal ions shuttled among Au(I)-catenates in the strong alkaline solution. Through the use of the microwave heating method, the spherical and cubic MNPs of various sizes and colors were synthesized. To fully utilize the polychrome MNPs, a visual sensor was constructed for the detection and discrimination of eight heavy metal ions. The fingerprint-like color response signals correspond to each heavy metal ion and can be distinguished using computer software. The detection limit (0.1 nM) of heavy metal ions discriminated by the sensor is significantly lower than the data reported. The validation of the sensor was carried out by quantitative detection of Hg2+ compared with its content in a certified reference material. This array method shows high sensitivity, good anti-interference, and potential in complex media.

The development of stabilized catalysts with one-dimensional meso-pore structures is important for advancing olefin polymerization. Covalent Organic Frameworks (COFs) are popular candidates for constructing single-site heterogeneous olefin polymerization catalysts due to their well-ordered structures and large channels. In this study, Zr-COF catalysts were applied for the first time to the production of ultra-high molecular weight (Mw = 1.71 x 106 g mol-1) linear polyethylene (UHMWPE) at 5 bar ethylene pressure, filling the gap of traditional catalysts for ethylene polymerization at low pressures. The microenvironment of nanoconfinement and electronic effects of Zr-COFs can directly affect the polymer properties, including product size, morphology, molecular weight and molecular weight distribution. Kinetic simulations show that a COF with a triazine ring skeleton can provide suitable receptors for forming hydrogen bonds to enrich ethylene monomers, leading to low-pressure ethylene polymerization. The continuous and uniform flow of monomers in the highly oriented channels lays a solid foundation for the full contact between the active centre and the monomer, which further facilitates the formation of conformational relationships. Zr-TtDa catalyst with a triazine ring in ethylene polymerization forms hydrogen bonds with ethylene, enriching it around metal sites. This method produced high molecular weight linear polyethylene (Mw = 1.71 x 106 g mol-1) at a low pressure (5 bar).

Carbon dioxide (CO2) is one of the main greenhouse gases and the major factor driving global climate change. From the viewpoint of abundance, economics, non-toxicity, and renewability, CO2 is an ideal and significant C1 resource, and its capture and recycling into fuels and chemical feedstocks using renewable energy is of great significance for the sustainable development of society. Electrochemical CO2 reduction reactions (CO2RRs) are an important pathway to utilize CO2 resources. Zinc has been demonstrated as an effective catalyst for CO2RRs. Numerous studies have focused on improving the efficiency of zinc-based catalysts by tuning their morphology and components, as well as controlling their oxidation states or doping. However, only a handful of reviews have evaluated the performance of Zn-based CO2RR electrocatalysts. The present review endeavors to fill this research gap and introduces the recent progress in using CO2RRs to create various fuels (carbon-containing substances or hydrocarbons) using zinc-based catalysts, including Zn monomers, Zn-containing bimetals, oxide-derived Zn catalysts, and single/dual Zn atom catalysts. The mechanism of the electroreduction reaction of CO2 is discussed. Based on the previous achievements, the current stage and the outlook for future developments in the field are summarized. This review will provide a reference for future research on CO2RRs to generate fuels using Zn-based catalysts and their commercialization.

以烯丙基氯和CO2为原料、Cu-In复合材料为工作电极、Mg为牺牲阳极,在一室型电解池中常温常压恒电流下电解合成3-丁烯酸.其中,Cu-In复合材料采用电镀方法制备,并利用XRD、SEM和EDX表征.为提高目标产物3-丁烯酸的产率,本文分析了阴极材料电镀时间、溶剂、支持电解质、电流密度、通电量和温度等因素对烯丙基氯电羧化反应的影响.在25℃反应温度、90minCu-In复合材料电镀时间、MeCN溶剂、四乙基碘化钱(TEAI)支持盐、3.0F/mol电解电量、8 mA cm2电流密度的优化条件下,3-丁烯酸的产率可达56％.此外,在优化条件下还考察了烯丙基溴、肉桂基氯、肉桂基溴、3-氯-2-甲基丙烯等烯丙基卤代物的电羧化反应,结果表明均可得到相应的羧酸,意味着Cu-In双金属电极对催化烯丙基卤代物电羧化反应具一定的普适性.

This work presents a facile strategy for the generation of Fe3O4@poly(4-vinylpyridine)-block-polystyrene (Fe3O4@P4VP-b-PS) magnetic polymer nanocomposites. P4VP-b-PS nanoparticles prepared by dispersion RAFT polymerization of styrene in methanol/water in the presence of macro-P4VP chain transfer agent was employed as templates to grow Fe3O4 on polymeric network templates. With the following addition of FeCl3 into the above polymer colloids, pyridyl moieties in P4VP block of nanoparticles could further react with Fe3+ through a coordination reaction to generate Fe3+@P4VP-b-PS nanoparticles. After the subsequent addition of FeCl2 and NH3 center dot H2O, the co-precipitation reaction occurred on the surface of the polymeric nanoparticle to form Fe3O4@P4VP-b-PS magnetic polymer nanocomposites. Herein, FT-IR, XRD, TGA, XPS, TEM and VSM were applied to characterize the morphology, structure and magnetism performance of the synthesized magnetic polymeric nanocomposites. [GRAPHICS] .

The majority of commercial polyolefins are produced by coordination polymerization using early or late transition metal catalysts. Molecular catalysts containing these transition metals (Ti, Zr, Cr, Ni, and Fe, etc.) are loaded on supports for controlled polymerization behavior and polymer morphology in slurry or gas phase processes. Within the last few years, metal-organic frameworks (MOFs), a class of unique porous crystalline materials constructed from metal ions/clusters and organic ligands, have been designed and utilized as excellent supports for heterogeneous polymerization catalysis whose high density and uniform distribution of active sites would benefit the modulations of molecular weight distributions of high-performance olefin oligomers and (co)polymers. Impressive efforts have been made to modulate the microenvironment surrounding the active centers at the atomic level for improved activities of MOFs-based catalysts and controlled selectivity of olefin insertion. This review aims to draw a comprehensive picture of MOFs for coordination olefin oligomerization and (co)polymerization in the past decades with respect to different transition metal active centers, various incorporation sites, and finally microenvironment modulation. In consideration of more efforts are needed to overcome challenges for further industrial and commercial application, a brief outlook is provided.

合成一种双(8-羟基喹啉)类有机配体H2L,利用1H-NMR、13C-NMR和ESI-MS对其结构进行表征;配体H2L分别与Cd(II)和Zn(II)发生离子反应,得到两种金属配合物[Cd4L3I2]·4DMF(1)和[Zn2LI2]·2DMSO(2);利用单晶X射线衍射(SXRD)、粉末X射线衍射(PXRD)和荧光光谱对两种金属配合物的精确结构和发光性能进行研究.结果表明:金属配合物1和2是链状配位聚合物,两种配合物具有不同的双核构建单元和链状排列结构,且皆有较好的晶相纯度;选择380 nm作为激发波长时,配合物1和2分别在580,568 nm处出现最大发射峰,与配体H2L相比,其发射峰发生明显的红移.

Correction for ‘Nickel-catalyzed electrocarboxylation of allylic halides with CO2’ by La-Xia Wu et al., New J. Chem., 2021, 45, 13137–13141, DOI: 10.1039/D1NJ02006D.

Nickel catalysts were synthesized and used for regioselective electrocarboxylation of allylic halides and atmospheric CO2. β,γ-Unsaturated carboxylic acids were obtained with moderate to good yield and good functional group tolerance.

Maple-ball-like Mg-Al layered double hydroxides (LDHs) were successfully prepared via a microwave-assisted heating method in the presence of ethylene glycol water as a solvent, and the synthesis efficiency was significantly improved through the design approach.The product was characterized by a series of techniques, including X-ray diffraction, Fourier transforms infrared spectroscopy, field emission scanning electron microscopy, thermogravimetric analysis, and Brunauer-Emmett-Teller.The as-synthesized Mg-Al LDHs display considerable adsorption performance for the cationic dye methylene orange from aqueous solution within extremely short processing time.This study offers a low-cost approach for the synthesis of an Mg-Al LDH material that could be used as an effective adsorbent for the removal of dyes from wastewater.

Herein, we report a novel method for the synthesis of Prussian blue/PB containing polymeric hybrid nanoparticles. This method employs poly(4-vinylpyridine)/P4VP stabilized polystyrene/PS nanoparticles as a template to define the position of Prussian blue product. In the first step, the templates of P4VP-stabilized polystyrene polymer nanoparticle were prepared by dispersion polymerization of styrene in methanol/water in the presence of macro-P4VP chain transfer agents. With the addition of sodium pentacyanoammineferroate(II) hydrate/[Fe(CN) 5 NH 3 ] 3− into dispersion, pyridyl moieties in P4VP in polymeric nanoparticles could react with [Fe(CN) 5 NH 3 ] 3− through a ligand exchange reaction. Subsequent metal coordination polymerization of Fe 3+ with ferrate confined within the surface of the nanoparticles led to the generation of monodispersed PB coated polymeric nanoparticles. The nanoparticles were characterized and confirmed by various modern techniques such as FT-IR, UV–Vis, TGA, XPS, TEM, SEM and AFM. The UV–Vis, FT-IR, TGA and XPS studies suggested Prussian blue was successfully coordinated with P4VP-PS polymers template according to our experimental design. The morphology studies indicated that spherical nanoparticles were obtained. In particular, the EDX mapping results clearly show that the iron element is evenly distributed on the nanoparticles. In addition, two parameters, including the amount of initiator and the amount of iron in the system, have important effects on the particle size and distribution. This experimental system we designed has great potential for the synthesis of metal containing polymeric nanoparticles with other compositions and morphologies, which offers many possibilities worthy of further exploration.

Porous hydroxyapatite (HA) matrices with high porosity were prepared through a high temperature sintering method by using HA powder as raw material, polystyrene (PS) microspheres as pore-forming agents and polyvinyl alcohol (PVA) solution as adhesive. The characterization of HA was carried out by a series of techniques including XRD, FT-IR, FESEM and BET, and showed that the morphology and structure of porous HA material were closely related to the amount of PS and PVA. The adsorption capability for Cu2+, Cd2+ and Pb2+ in aqueous solution showed that the porous HA possessed a selective and strong uptake of Pb2+ ions and the adsorption efficiency reached 99.8% in 10 min.

羟基磷灰石(Hydroxyapatite,HAP)材料具有优良的骨传导性和生物相容性.为提高该类材料在生物及医学上的抗菌性能,银掺杂是可供选择的方法之一.本研究选择溶液沉淀法来合成银掺杂HAP,通过调节掺杂剂的浓度获得了单相结构的羟基磷灰石材料,讨论了银离子浓度对晶体结晶度和晶格参数产生的影响,以期为该类材料的后续应用提供实践基础.

This work presents a simple and facile strategy for the creation of Prussian blue containing polymeric nanocapsules. An crosslinked inverse miniemulsion with a formula of water/ K4Fe(CN)6/1,2-bis-(-2-iodoethyl) ethane(BIEE)/ toluene/ PDMAEMA-b-PS stabilizer mixture was prepared as soft template firstly. A crosslinking nanocapsule structure with K4Fe(CN)6 in water core could be achieved by a crosslinking reaction between PDMAEMA-b-PS stabilizers and BIEE. Upon the following addition of FeCl3 ether solution into the oil phase of this inverse miniemulsion, a coordination reaction between two iron salts occurred immediately to form a Prussian blue complex. Due to the solubility limitation of FeCl3 in the oil phase of the miniemulsion, forcing the coordination reaction of K4Fe(CN)6 and FeCl3 mainly occurred at the oil-water interface of the nanocapsules, resulting in a soft polymer/Prussian blue(PB) hybrid nanocapsule.

An active catalyst, [Cu]@Ag composite, was synthesized for the first time and used as a cathode for electrocarboxylation of cinnamyl chloride with CO2. β,γ-Unsaturated carboxylic acids were obtained with excellent yield and moderate selectivity. Moreover, reasonable yields and selectivities of carboxylic acids were also achieved with several allylic halides and aryl halides.

Developing a simple morphology-controlled synthesis of metastable vaterite is a goal in the field of materials research. In this paper, we successfully synthesized flower-like dendritic vaterite crystals using a microwave method with 2-naphthaleneacetic acid (2-NAA) and ethylene glycol (EG) as the regulating additives. The results show that the morphology of vaterite could be regulated by inducing a monolayer or multilayer flower-like structure with the appropriate choice of regulators. Interestingly, the microstructure analysis showed that such flower-like vaterite dendrites host two different kinds of crystal cells. The negative carbonate 2-NAA effectively neutralized the charge of the vaterite (001) plane, resulting in the crystalline growth along the direction parallel to it and inducing a flower-like morphology. This experiment reveals an alternative approach to controlling hierarchical structures during the synthesis of similar classes of minerals.