Nano Research最新文献

The importance of the oxygen reduction reaction (ORR) in fuel cells and zinc-air batteries is self-evident, and effective catalysts could significantly improve the catalytic efficiency of ORR. Single-atom catalysts are gaining increasing interest due to their high atom efficiency and effective catalytic performance compared to other catalyst types. While the optimal loading of catalytic sites in single-atom catalysts significantly influences their catalytic efficiency. However, creating stable single-atom catalysts with high-loading remains a difficult task. Therefore, we showcase and describe the latest developments in techniques for producing single-atom catalysts with high-loadings. In addition, the performance of noble metal, non-precious metal, and diatomic catalysts in ORR processes is summarized. What’s more, the key difficulties and opportunities in the sector are demonstrated by examining the synthesis techniques and evaluating the performance and structure. This review will help researchers to advance the research process of high-loading single-atom catalysts and accelerate their practical application in the field of ORR research.

The rapid quantification of hydroxyl radical (·OH) in real samples is a great challenge due to its highly reactive nature and the potential interferences from other coexisting reactive oxygen species (ROS). Herein, a chemiluminescence (CL) probe (ox-CDs) was rationally developed for the detection of ·OH through controlled oxidation treatment of original CDs (o-CDs) with H₂O₂. Post-oxidation of CDs can reduce the surface defects or functional groups on the CDs, exposing reactive sites capable of effectively reacting with ·OH. The chemical energy generated from redox reaction between ·OH and the ox-CDs can be efficiently utilized to generate strong and selective CL responses to ·OH without interferences from other ROS. Thus, a highly selective and sensitive CL method with a linear range from 0.01 to 150 μM and a detection limit of 3 nM was developed, which was successfully applied for monitoring the ·OH production from cigarette and mosquito coil smoke.

The selective oxidation of hydrocarbons can be used to produce oxygen-containing functional compounds such as alcohols, aldehydes or ketones and its efficient and green conversion lies in the development of efficient catalysts that activate C-H bonds and O₂ simultaneously. In this work, the bimetallic organic framework (CoMnBDC) material with morphology of stacked nanosheets was synthesized using terephthalic acid as ligands to coordinate with Co²⁺ and Mn²⁺ cations under solvothermal conditions. As revealed by spectroscopic characterizations, the electron transfer from Mn to Co in the CoMnBDC resulted in the reduction of the Co average oxidation state and increase of the Mn average oxidation state. The CoMnBDC nanosheets were used as catalyst in catalytic oxidation of ethylbenzene, in which the redox effect promotes the effective electron transfer, the activation of O₂ and benzyl C-H bond. The 96.2% conversion of ethylbenzene and 98.0% selectivity towards acetophenone could be obtained with oxygen as sole oxidant and solvent-free condition. The excellent catalytic performance is related to the structure of CoMnBDC and is also the best when compared with reported results. Various types of aromatic hydrocarbons containing benzyl C-H bonds can be effectively oxidized by CoMnBDC to produce corresponding ketone products. The density functional theory (DFT) calculation revealed that the redox effect leads to the relative enrichment of electrons on Co in CoMnBDC, which is conducive to the activation of O₂; Mn with higher oxidation state is beneficial for the adsorption of ethylbenzene and activation of C-H bonds. The CoMnBDC has a lower energy barrier for transition state, making it easier for the ethylbenzene oxidation to produce acetophenone.

The bimetallic nickel-cobalt phosphide (NiCoP) has been confirmed as an efficient electrocatalyst in water splitting. But little attention is paid to the selectivity and affinity of metal sites on hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, we report a trace-Zn-doping (2.18 wt.%) NiCoP (Zn-NiCoP) whereby the nanoparticles self-aggregated to form elongated nanoneedles. We discover that both Co and Ni sites can be replaced by Zn. The Co substitution improves HER, while the Ni substitution dramatically reduces the energy barrier of the rate-determining step (*O → *OOH). The negative shift of d-band centers after Zn doping ameliorates the intermediate desorption. Therefore, Zn-NiCoP demonstrates superior electrocatalytic activity with overpotentials of 48 and 240 mV for HER and OER at 10 and 50 mA·cm⁻², respectively. The cell voltage with Zn-NiCoP as both anode and cathode in water splitting was as low as 1.35 V at 10 mA·cm⁻².

Compared to nanostructured Si/C materials, micro-sized Si/C anodes for lithium-ion batteries (LIBs) have gained significant attention in recent years due to their higher volumetric energy density, reduced side reactions and low costs. However, they suffer from more severe volume expansion effects, making the construction of stable micro-sized Si/C anode materials crucial. In this study, we proposed a simple wet chemistry method to obtain porous micro-sized silicon (μP-Si) from waste AlSi alloys. Then, the μP-Si@carbon nanotubes (CNT)@C composite anode with high tap density was prepared by wrapping with CNT and coated with polyvinylpyrrolidone (PVP)-derived carbon. Electrochemical tests and finite element (FEM) simulations revealed that the introduction of CNTs and PVP-derived carbon synergistically optimize the stability and overall performance of the μP-Si electrode via construction of tough composite interface networks. As an anode material for LIBs, the μP-Si@CNT@C electrode exhibits boosted reversible capacity (∼ 3500 mAh·g⁻¹ at 0.2 A·g⁻¹), lifetime and rate performance compared to pure μP-Si. Further full cell assembly and testing also indicates that μP-Si@CNT@C is a highly promising anode, with potential applications in future advanced LIBs. It is expected that this work can provide valuable insights for the development of micro-sized Si-based anode materials for high-energy-density LIBs.

Optimizing the catalytic activity and stability of molybdenum disulfide (MoS2) towards alkaline hydrogen evolution reaction (HER) is significant for sustaining green hydrogen. A moderate localized electronic structure of active sites plays a crucial role in determining the activity and stability of the catalysts, yet how to construct such localized electronic structure still remains indeterminacy. Enlightened by theoretical prediction, herein, the introduction of both single-atom Re and the adjacent S vacancy in MoS₂ (denoted as Re-MoS₂-Vs) exhibits collaborative effect on regulating the localized electronic structure of active sites (viz. Re-(S, Vs)-Mo). Such regulated electronic structure helps to decrease the energy barrier of the water dissociation and optimize hydrogen adsorption energy for enhancing alkaline HER performance. Most importantly, Mo-S bonds in the above local Re-(S, Vs)-Mo configurations are also strengthened for preventing the leaching of Mo and S atoms and then ensuring the long-time stability. Consequently, the deliberately designed Re-MoS₂-Vs with a Re coordination number of ~ 5.0 is experimentally verified to exhibit a comparable electrocatalytic performance and robust operational stability over 120 h. This strategy provides a promising guidance for modulating the electronic structure of MoS2 based catalysts via double-tuning atomic-scale local configuration for HER applications.

Integrating hierarchical plasmonic cavities into photocatalysis offers a promising avenue for expanding the light utilization range to cover the entire solar spectrum. However, fabricating these nanostructures with seamless size transitions for a wide plasmon resonant range remains technically challenging, requiring precise nanofabrication control and often relying on expensive and laborious techniques like e-beam lithography and reactive ion etching. Herein, a one-step forming strategy was explored to fabricate simple yet hierarchical plasmonic cavities featuring the surface nanodome array-integrated plasmonic Fabry–Pérot cavity through a facile large-area nanoimprinting method. This design leverages a uniform feature size and periodic arrangement to broaden the light utilization range of TiO₂ across the entire solar spectrum (200–2500 nm). It consists of an upper nanodome array cavity with vertically continuous graded sizes for broadband absorption (200–1500 nm), coupled with a bottom plate cavity that enlarges the overall cavity size to extend the range to 2500 nm. Remarkably, simply adjusting the thickness of the plate cavity can tune the resonant position, eliminating the need for expensive mold modifications. When combined with TiO₂, this hierarchical plasmonic cavity significantly enhances the photocatalytic hydrogen evolution rate to 36.3 µmol/h, achieving a remarkable 9.8-fold increase compared to pure TiO₂ under full-spectrum illumination. This approach offers a convenient and inexpensive alternative to sophisticated nanofabrication techniques for large-area hierarchical plasmonic cavities with broadband plasmon resonance to enhance the photocatalytic hydrogen evolution.

Pristine tin (Sn) and tin dioxide (SnO₂) have sparked wide interest owing to their abundant resources and superior theoretical capacity. Nevertheless, the obvious volume expansion effect upon cycling and undesirable conductivity of Sn-based materials lead to undesirable specific capacity. In this work, a nanostructured Sn/SnO₂/nitrogen-doped carbon (NC) superstructure was prepared through a facile electrospray-carbonization strategy. The Sn/SnO₂ nanoparticles (NPs) were uniformly dispersed in a spherical NC matrix, which prevented the volume expansion and aggregation of NPs and facilitated the ion diffusion and charge transfer kinetics. When the optimized Sn/SnO₂/NC superstructures were employed as lithium-ion battery anodes, a remarkable specific capacity of 747.9 mAh·g⁻¹ over 200 cycles at 0.5 A·g⁻¹ and a superior cyclability of 644.1 mAh·g⁻¹ over 1000 cycles at 2 A·g⁻¹ were obtained. This effective synthetic strategy for synthesizing superstructures provides valuable insights for the advancement of lithium-ion batteries.

This review highlights the critical effects of heat transfer and bubble mass transfer in alkaline water electrolysis on hydrogen generation efficiency. To improve heat transfer performance, the study focuses on reducing electrical resistance and controlling the electrolysis system’s temperature. It proposes innovative strategies such as using metal matrix composites and catalysts to optimize electrode structure, precise temperature and pressure regulation and enhanced electrolyte concentration. Additionally, the study examines the dynamics of bubble mass transfer, proposing effective strategies to reduce bubble coverage, including hydrophilic electrodes, mechanically circulating the electrolyte and voltage smoothing with pressure swinging. This study contributes to the advancement of hydrogen energy technology with practical strategies. By adjusting the electrolysis system to optimize the combined effect of these factors, we can improve the efficiency, economy and environmental friendliness of hydrogen production. This will contribute to the transformation of the global energy mix and the implementation of sustainable development strategies.

Assembly of two-dimensional (2D) nanomaterials into well-organized architectures is pivotal for controlling their function and enhancing performance. As a promising class of 2D nanomaterials, MXenes have attracted significant interest for use in wearable electronics due to their unique electrical and mechanical properties. However, facile approaches for fabricating MXenes into macroscopic fibers with controllable structures are limited. In this study, we present a strategy for easily spinning MXene fibers by incorporating polyanions. The introduction of poly(acrylic acid) (PAA) into MXene colloids has been found to alter MXene aggregation behavior, resulting in a reduced concentration threshold for lyotropic liquid crystal phase. This modification also enhances the viscosity and shear sensitivity of MXene colloids. Consequently, we were able to draw continuous fibers directly from the gel of MXene aggregated with PAA. These fibers exhibit homogeneous diameter and high alignment of MXene nanosheets, attributed to the shear-induced long-range order of the liquid crystal phase. Furthermore, we demonstrate proof-of-concept applications of the ordered MXene fibers, including textile-based supercapacitor, sensor and electrical thermal management, highlighting their great potential applied in wearable electronics. This work provides a guideline for processing 2D materials into controllable hierarchical structures by regulating aggregation behavior through the addition of ionic polymers.