One‐Step Synthesis of Monodispersed Mesoporous Carbon Nanospheres for High‐Performance Flexible Quasi‐Solid‐State Micro‐Supercapacitors

Cost‐effective synthesis of carbon nanospheres with a desirable mesoporous network for diversified energy storage applications remains a challenge. Herein, a direct templating strategy is developed to fabricate monodispersed N‐doped mesoporous carbon nanospheres (NMCSs) with an average particle size of 100 nm, a pore diameter of 4 nm, and a specific area of 1093 m² g^?1. Hexadecyl trimethyl ammonium bromide and tetraethyl orthosilicate not only play key roles in the evolution of mesopores but also guide the assembly of phenolic resins to generate carbon nanospheres. Benefiting from the high surface area and optimum mesopore structure, NMCSs deliver a large specific capacitance up to 433 F g^?1 in 1 m H₂SO₄. The NMCS electrodes–based symmetric sandwich supercapacitor has an output voltage of 1.4 V in polyvinyl alcohol/H₂SO₄ gel electrolyte and delivers an energy density of 10.9 Wh kg^?1 at a power density of 14014.5 W kg^?1. Notably, NMCSs can be directly applied through the mask‐assisted casting technique by a doctor blade to fabricate micro‐supercapacitors. The micro‐supercapacitors exhibit excellent mechanical flexibility, long‐term stability, and reliable power output.     

Space‐Confined Synthesis of ZIF‐67 Nanoparticles in Hollow Carbon Nanospheres for CO2 Adsorption

Herein, the design and synthesis of ZIF‐67 nanoparticles (NPs) with tunable size grown inside hollow carbon nanospheres (ZIF‐67@HCSs) via a space‐confined strategy is reported. HCSs are first prepared via pyrolysis of polystyrene@polypyrrole (PS@PPy) composite nanospheres. Further infiltration of 2‐methylimidazole (MI) into the HCSs (MI@HCSs) using a melting‐diffusion strategy, followed by immersing MI@HCSs into Co(NO₃)₂ solution through the pores and channels of HCSs results in the formation of ZIF‐67@HCSs. The as‐synthesized ZIF‐67@HCSs with tunable ZIF‐67 size is achieved by changing the amount of MI. Due to the high pore volume provided by nanoscale ZIF‐67 NPs, the as‐prepared core–shell ZIF‐67@HCSs exhibit outstanding adsorption capacity for CO₂.     

A General and Straightforward Route to Noble Metal‐Decorated Mesoporous Transition‐Metal Oxides with Enhanced Gas Sensing Performance

Controllable and efficient synthesis of noble metal/transition‐metal oxide (TMO) composites with tailored nanostructures and precise components is essential for their application. Herein, a general mercaptosilane‐assisted one‐pot coassembly approach is developed to synthesize ordered mesoporous TMOs with agglomerated‐free noble metal nanoparticles, including Au/WO₃, Au/TiO₂, Au/NbO_x, and Pt/WO₃. 3‐mercaptopropyl trimethoxysilane is applied as a bridge agent to cohydrolyze with metal oxide precursors by alkoxysilane moieties and interact with the noble metal source (e.g., HAuCl₄ and H₂PtCl₄) by mercapto (? SH) groups, resulting in coassembly with poly(ethylene oxide)‐b‐polystyrene. The noble metal decorated TMO materials exhibit highly ordered mesoporous structure, large pore size (≈14–20 nm), high specific surface area (61–138 m² g^?1), and highly dispersed noble metal (e.g., Au and Pt) nanoparticles. In the system of Au/WO₃, in situ generated SiO₂ incorporation not only enhances their thermal stability but also induces the formation of ε‐phase WO₃ promoting gas sensing performance. Owning to its specific compositions and structure, the gas sensor based on Au/WO₃ materials possess enhanced ethanol sensing performance with a good response (R_air/R_gas = 36–50 ppm of ethanol), high selectivity, and excellent low‐concentration detection capability (down to 50 ppb) at low working temperature (200 °C).     

Ultrasmall Particle Sizes of Walnut‐Like Mesoporous Silica Nanospheres with Unique Large Pores and Tunable Acidity for Hydrogenating Reaction

The large particle sizes, inert frameworks, and small pore sizes of mesoporous silica nanoparticles greatly restrict their application in the acidic catalysis. The research reports a simple and versatile approach to synthesize walnut‐like mesoporous silica nanospheres (WMSNs) with large tunable pores and small particle sizes by assembling with Beta seeds. The as‐synthesized Beta‐WMSNs composite materials possess ultrasmall particulate sizes (70 nm), large radial mesopores (≈30 nm), and excellent acidities (221.6 mmol g^?1). Ni₂P active phase is supported on the surface of Beta‐WMSNs composite materials, and it is found that the obtained composite spherical materials can reduce the Ni₂P particle sizes from 8.4 to 4.8 nm with the increasing amount of Beta seeds, which can provide high accessibilities of reactants to the active sites. Furthermore, the unique large pores and ultrasmall particle sizes of Beta‐WMSNs samples facilitate the reduction of the diffusion resistance of reactants due to the short transporting length, thus the corresponding Ni₂P/Beta‐WMSNs composite catalysts show the excellent hydrogenating activity compared to the pure Ni₂P/WMSNs catalyst.     

Mesoporous Nitrogen‐Doped Carbon Nanospheres as Sulfur Matrix and a Novel Chelate‐Modified Separator for High‐Performance Room‐Temperature Na‐S Batteries

Room‐temperature sodium‐sulfur (RT/Na‐S) batteries are considered among the most promising next‐generation energy storage and conversion systems because of the earth‐abundant reserves of sodium and sulfur. These batteries also possess the advantages of high theoretical gravimetric capacity, high energy density, and low cost. Herein, highly uniform Fe³⁺/polyacrylamide nanospheres (FPNs) are fabricated on a large‐scale by a facile, low‐cost approach. Subsequently, mesoporous nitrogen‐doped carbon nanospheres (PNC‐Ns), obtained by carbonizing FPNs, are applied as a sulfur matrix to improve the utilization of sulfur, enhance the overall conductivity of the cathode, and inhibit the shuttling of sodium polysulfides (SPSs). In addition, graphene and FPNs are simultaneously coated onto the side of the separator to form a FPNs‐graphene‐functionalized separator (FPNs‐G/separator); here, the mesoporous FPNs effectively anchor and block the SPSs, while the large specific area graphene sheets eliminate the intrinsic mechanical brittleness of the FPNs and improve the overall conductivity of RT/Na‐S batteries. When S/PNC‐Ns as a cathode and FPNs‐G/separator are assembled into an RT/Na‐S battery, it delivers a high discharge capacity (639 mAh g^‐1 at 0.1 C after 400 cycles), stable cycle life (396 mAh g^‐1 at 0.5 C after 800 cycles), and good rate performance (228 mAh g^‐1 at 2 C).     

Noble‐Metal‐Free Electrocatalysts for Oxygen Evolution

Oxygen evolution reaction (OER) plays a vital role in many energy conversion and storage processes including electrochemical water splitting for the production of hydrogen and carbon dioxide reduction to value‐added chemicals. IrO₂ and RuO₂, known as the state‐of‐the‐art OER electrocatalysts, are severely limited by the high cost and low earth abundance of these noble metals. Developing noble‐metal‐free OER electrocatalysts with high performance has been in great demand. In this review, recent advances in the design and synthesis of noble‐metal‐free OER electrocatalysts including Ni, Co, Fe, Mn‐based hydroxides/oxyhydroxides, oxides, chalcogenides, nitrides, phosphides, and metal‐free compounds in alkaline, neutral as well as acidic electrolytes are summarized. Perspectives are also provided on the fabrication, evaluation of OER electrocatalysts and correlations between the structures of the electrocatalysts and their OER activities.     

Ligand‐Free Fe3O4/CMCS Nanoclusters with Negative Charges for Efficient Structure‐Selective Protein Adsorption

The easy and effective capture of a single protein from a complex mixture is of great significance in proteomics and diagnostics. However, adsorbing nanomaterials are commonly decorated with specific ligands through a complicated and arduous process. Fe₃O₄/carboxymethylated chitosan (Fe₃O₄/CMCS) nanoclusters are developed as a new nonligand modified strategy to selectively capture bovine hemoglogin (BHB) and other structurally similar proteins (i.e., lysozyme (LYZ) and chymotrypsin (CTP)). The ligand‐free Fe₃O₄/CMCS nanoclusters, in addition to their simple and economical two‐step preparation process, possess many merits, including uniform morphology, high negative charges (?27 mV), high saturation magnetization (60 emu g^?1), and high magnetic content (85%). Additionally, the ligand‐free Fe₃O₄/CMCS nanoclusters are found to selectively capture BHB in a model protein mixture even within biological samples. The reason for selective protein capture is further investigated from nanomaterials and protein structure. In terms of nanomaterials, it is found that high negative charges are conducive to selectively adsorb BHB. In consideration of protein structure, interestingly, the ligand‐free magnetic nanoclusters display a structure‐selective protein adsorption capacity to efficiently capture other proteins structurally similar to BHB, such as LYZ and CTP, showing great potential of the ligand‐free strategy in biomedical field.     

Facile Synthesis of Macrocellular Mesoporous Foamlike Ce–Sn Mixed Oxides with a Nanocrystalline Framework by Using Triblock Copolymer as the Single Template

Macrocellular mesoporous foamlike cerium–tin mixed oxide materials with well‐defined porous structure and nanocrystalline frameworks are synthesized through a simple one‐step self‐assembly process using an amphiphilic triblock copolymer as the single template. The macrocellular pores are synthesized without the addition of any swelling agent or hazardous acids. The final mixed oxide possesses a hierarchically porous structure including macrocellular foam with ultralarge cell size, closed windows, and mesopores on the walls. This indicates that the porous structure can be notably stabilized and improved by the incorporation of Sn in the CeO₂. The materials are expected to be good candidates in catalysis, since the hierarchical porosity enables high surface areas and hence more chemically active sites associated with the mesopores, combined with the high efficiency of mass transport from the macrocellular foam. The catalytic characteristics are discussed in relation to the architectures of the materials, and it is revealed that the macrocellular/mesoporous materials would be an efficient catalyst for CO oxidation.