Molybdenum Dioxide Nanoparticles Anchored on Nitrogen-Doped Carbon Nanotubes as Oxidative Desulfurization Catalysts: Role of Electron Transfer in Activity and Reusability

Electron transfer between metal-oxides and supports considerably affects the oxidative desulfurization (ODS) performance of catalysts, while this is far from being well understood. Herein, molybdenum dioxide with oxygen vacancies (V_O-MoO₂) catalysts derived from Mo-based metal-organic frameworks are anchored on electron-rich nitrogen-doped carbon nanotubes (NC) to obtain excellent ODS activity and reusability. Results show that either dibenzothiophene (DBT) or 4,6-dimethyldibenzothiophene (4,6-DMDBT) is removed 100% on the composite catalyst (V_O-MoO₂@NC) within 40 min of reaction when cumene hydroperoxide is chosen as an oxidant. After five cycles of reaction, DBT and 4,6-DMDBT removal still exceeded 99.5 and 95.0%, respectively. Results from density functional theory calculations and characterizations confirm that the strong electron-donating effect of NC on V_O-MoO₂ can promote the dispersion of V_O-MoO₂ and reduce the bond energy of the Mo O bond, leading to exposure of active sites and enrichment of oxygen vacancies (V_O). Furthermore, the strong interfacial electrostatic interaction caused by the electron transfer from NC to V_O-MoO₂ can reduce the leaching of active sites of the catalyst. This study provides a versatile strategy of constructing strong electronic interaction between metal-oxide and support via anchoring on NC for the design of high-performance ODS catalysts.     

Molybdenum Phosphide/Carbon Nanotube Hybrids as pH‐Universal Electrocatalysts for Hydrogen Evolution Reaction

Molybdenum phosphide (MoP) has received increasing attention due to its high catalytic activity in hydrogen evolution reaction (HER). However, it remains difficult to construct well‐defined MoP nanostructures with large density of active sites and high intrinsic activity. Here, a facile and general method is reported to synthesize an MoP/carbon nanotube (CNT) hybrid featuring small‐sized and well‐crystallized MoP nanoparticles uniformly coated on the sidewalls of multiwalled CNT. The MoP/CNT hybrid exhibits impressive HER activities in pH‐universal electrolytes, and requires the overpotentials as low as 83, 102, and 86 mV to achieve a cathodic current density of 10 mA cm^?2 in acidic 0.5 m H₂SO₄, neutral 1 m phosphate buffer solution, and alkaline 1 m KOH electrolytes, respectively. It is found that the crystallinity of MoP has significant influence on HER activity. This study provides a new design strategy to construct MoP nanostructures for optimizing its catalytic performance.     

Towards Efficient Dispersion of Carbon Nanotubes in Thermotropic Liquid Crystals

Motivated by numerous recent reports indicating attractive properties of composite materials of carbon nanotubes (CNTs) and liquid crystals (LCs) and a lack of research aimed at optimizing such composites, the process of dispersing CNTs in thermotropic LCs is systematically studied. LC hosts can perform comparably or even better than the best known organic solvents for CNTs such as N‐methyl pyrrolidone (NMP), provided that the dispersion process and choice of LC material are optimized. The chemical structure of the molecules in the LC is very important; variations in core as well as in terminal alkyl chain influence the result. Several observations moreover indicate that the anisotropic nematic phase, aligning the nanotubes in the matrix, per se stabilizes the dispersion compared to a host that is isotropic and thus yields random tube orientation. The chemical and physical phenomena governing the preparation of the dispersion and its stability are identified, taking into account enthalpic, entropic, as well as kinetic factors. This allows a guideline on how to best design and prepare CNT–LC composites to be sketched, following which tailored development of new LCs may take the advanced functional material that CNT–LC composites comprise to the stage of commercial application.     

Atomic Ni Anchored Covalent Triazine Framework as High Efficient Electrocatalyst for Carbon Dioxide Conversion

Electrochemically driven carbon dioxide (CO₂) conversion is an emerging research field due to the global warming and energy crisis. Carbon monoxide (CO) is one key product during electroreduction of CO₂; however, this reduction process suffers from tardy kinetics due to low local concentration of CO₂ on a catalyst's surface and low density of active sites. Herein, presented is a combination of experimental and theoretical validation of a Ni porphyrin‐based covalent triazine framework (NiPor‐CTF) with atomically dispersed NiN₄ centers as an efficient electrocatalyst for CO₂ reduction reaction (CO₂RR). The high density and atomically distributed NiN₄ centers are confirmed by aberration‐corrected high‐angle annular dark field scanning transmission electron microscopy and extended X‐ray absorption fine structure. As a result, NiPor‐CTF exhibits high selectivity toward CO₂RR with a Faradaic efficiency of >90% over the range from ?0.6 to ?0.9 V for CO conversion and achieves a maximum Faradaic efficiency of 97% at ?0.9 V with a high current density of 52.9 mA cm^?2, as well as good long‐term stability. Further calculation by the density functional theory method reveals that the kinetic energy barriers decreasing for *CO₂ transition to *COOH on NiN₄ active sites boosts the performance.     

Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

In Situ Carbon Insertion in Laminated Molybdenum Dioxide by Interlayer Engineering Toward Ultrastable “Rocking-Chair” Zinc-Ion Batteries

Aqueous zinc-ion batteries (ZIBs) have attracted significant attention due to their intrinsic safety, cost-effectiveness, and environmental friendliness. However, the common zinc metal anode suffers from zinc dendrite formation, self-corrosion, and surface passivation, which impede the further application of aqueous ZIBs. Herein, carbon-inserted molybdenum dioxide (MoO₂) materials with laminated structure are designed as novel intercalation-type anodes for ZIBs by combination of interlayer engineering and in situ carbonization of aniline guest in molybdenum trioxide interlayers. The uniform dispersion of carbon layers in laminated MoO₂ not only provide fast transportation paths for electron but also strengthen the framework of MoO₂, leading to high structural integration during high-rate cycling. Benefiting from the unique structural design, the carbon-inserted MoO₂ electrode exhibits high initial Coulombic efficiency, excellent cycling stability, and outstanding rate capability. Multiple ex situ characterizations reveal its excellent electrochemical stability is derived from reversible intercalation mechanism and ultrastable structural framework. Furthermore, the rocking-chair zinc-ion full battery assembled with the zinc pre-intercalated Na₃V₂(PO₄)₂O₂F cathode presents excellent stability and ultralong lifespan with a high capacity retention of 91% over 8000 cycles.     

Single-Walled Carbon Nanotube Film as an Efficient Conductive Network for Si-Based Anodes

Silicon-based anodes are considered ideal candidate materials for next-generation lithium-ion batteries due to their high capacity. However, the low conductivity and large volume variations during cycling inevitably result in inferior cyclic stability. Herein, a dry method without binders is designed to fabricate Si-based electrodes with single-walled carbon nanotubes (SWCNTs) network and to explore the different mechanisms between SWCNT and multiwalled carbon nanotubes (MWCNTs) as a conductive network. As expected, higher initial discharge capacity (1785 mAh g⁻¹), higher initial Coulombic efficiency (ICE, 81.52%) and outstanding cyclic stability are obtained from the SiO_x@C|SWCNT anodes. Furthermore, its lithium-ion diffusion coefficient (D_Li+) is 3–4 orders of magnitude higher than that of SiO_x@C|MWCNT. The underlying mechanism is clarified by in situ Raman spectroscopy and theoretical analysis. It is found that the SWCNTs can maintain good contact with SiO_x@C even under tensile stresses up to 6.2 GPa, while the MWCNTs lose electrical contact due to alternating compressive stress up to 8.9 GPa and tensile stress up to 2.5 GPa during long-term cycling. Under such very large stresses, the more flexible SWCNTs and their stronger van der Waals forces ensure that SiO_x@C still has good contact with SWCNTs.     

Robust Biocatalysts Displayed on Crystalline Protein-Layered Cells for Efficient and Sustainable Hydration of Carbon Dioxide

Mineral carbonation is the most effective carbon capture technique, but carbon dioxide (CO₂) conversion is limited by the slow hydration rate of CO₂ (<10⁻¹ s⁻¹). A biological solution exists: carbonic anhydrase (CA) efficiently hydrates CO₂ at a turnover rate of ≈10⁶ s⁻¹ under ambient conditions, making it an extremely attractive candidate for industrial post-combustion CO₂ capture. However, high cost and poor long-term stability impose a technical barrier to its practical uses. Here, a genetically engineered Corynebacterium glutamicum (C. glutamicum) is introduced as a robust cell display platform for the in situ stabilization and low-cost production of CA. The enzyme is displayed in the mycolic layer with porin B as an anchoring protein with (GGGGS)₂ as a spacer. The cell-displayed CA exhibits no significant inactivation of the CO₂ hydration activity for at least one month at 37 °C. Its denaturation rate constant at 50 °C (0.07) is an order of magnitude lower than that of free CA (0.52–0.54). This study demonstrates that a structurally robust cell template allows the effective stabilization of CA, suggesting the C. glutamicum-based cell display as a promising technique to achieve highly efficient, sustainable, and low-cost CO₂ capture for industrial applications.     

Stabilizing Active Edge Sites in Semicrystalline Molybdenum Sulfide by Anchorage on Nitrogen‐Doped Carbon Nanotubes for Hydrogen Evolution Reaction

Finding an abundant and cost‐effective electrocatalyst for the hydrogen evolution reaction (HER) is crucial for a global production of hydrogen from water electrolysis. This work reports an exceptionally large surface area hybrid catalyst electrode comprising semicrystalline molybdenum sulfide (MoS_2+x) catalyst attached on a substrate based on nitrogen‐doped carbon nanotubes (N‐CNTs), which are directly grown on carbon fiber paper (CP). It is shown here that nitrogen‐doping of the carbon nanotubes improves the anchoring of MoS_2+x catalyst compared to undoped carbon nanotubes and concurrently stabilizes a semicrystalline structure of MoS_2+x with a high exposure of active sites for HER. The well‐connected constituents of the hybrid catalyst are shown to facilitate electron transport and as a result of the good attributes, the MoS_2+x/N‐CNT/CP electrode exhibits an onset potential of ?135 mV for HER in 0.5 m H₂SO₄, a Tafel slope of 36 mV dec^?1, and high stability at a current density of ?10 mA cm^?2.     

A Type of 1 nm Molybdenum Carbide Confined within Carbon Nanomesh as Highly Efficient Bifunctional Electrocatalyst

Highly efficient platinum‐alternative bifunctional catalysts by using abundant non‐noble metal species are of critical importance to the future sustainable energy reserves. Unfortunately, current electrocatalysts toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) are far from satisfactory because of lacking reasonable design and assembly protocols. A type of 1‐nm molybdenum carbide nanoparticles confined in mesh‐like nitrogen‐doped carbon (Mo₂C@NC nanomesh) with high specific surface area is reported here. In addition to the superior ORR performance comparable to platinum, the catalyst offers a high HER activity with small Tafel slope of 33.7 mV dec^?1 and low overpotential of 36 mV to reach ?10 mA cm^?2. Theoretical calculations indicate that the active sites of the catalyst are mainly located at Mo atoms adjacent to the N‐doped carbon layer, which contributes the high HER activity. These findings show the great potential of Mo₂C species in wide electrocatalysis applications.     

Metal‐Organic Precursor–Derived Mesoporous Carbon Spheres with Homogeneously Distributed Molybdenum Carbide/Nitride Nanoparticles for Efficient Hydrogen Evolution in Alkaline Media

The generation of hydrogen through water electrolysis is considered as a sustainable approach for future fuel production. Molybdenum (Mo)‐based compounds are reported as highly active and inexpensive alternatives to platinum‐based electrocatalysts for the hydrogen evolution reaction (HER). Currently, the major challenge for Mo‐based HER electrocatalysts lies in establishing new concepts of micro‐/nanostructure design to enhance the hydrogen evolution kinetics and realizing facile, large‐scale, and green fabrication processes. Here, a fast, scalable, and eco‐friendly metal‐organic coordination precursor–assisted strategy is reported for synthesizing novel hierarchically mesoporous Mo‐based carbon electrocatalysts for efficient hydrogen production. Benefiting from homogeneously distributed Mo‐based nanocrystallites/heterojunctions and uniform mesopores, the Mo‐based mesoporous electrocatalyst shows high hydrogen evolution activity and stability with a low overpotential of 222 mV at 100 mA cm^?2 (Pt/C: 263 mV), ranging among the best non‐noble metal HER catalysts in alkaline condition. Overall, the discovery of using dopamine–molybdate coordination precursor with silica nanoparticles will not only create a new pathway for controllable synthesis of diverse kinds of micro‐/nanostructured Mo‐based catalysts, but also take a step toward the fast and scale‐up production of advanced mesoporous carbon electrodes for a broad range of applications.     

大电流密度碳纳米管阴极的生长及场发射性能研究

研究了碳纳米管作为大电流密度场发射阴极的CVD生长情况与场发射性能。结果表明,通过CVD生长的碳纳米臂的直径与催化剂颗粒的直径相近,其生长方向是随机的。根据薄膜厚度与催化剂颗粒的关系,认为通过控制催化剂薄膜的厚度可能会达到调节碳纳米管直径的目的。在实验中获得的碳纳米管具备了良好的场发射性能,在直径为0．13mm的圆形面积上获得的碳纳米管场发射平均电流密度达到1．28A／cm^2。     

CO2激光犬膀胱粘膜剥脱术的实验研究

目的:探讨CO2激光犬膀胱粘膜剥脱术的可行性与安全性。方法:开放手术条件下,采用经多晶锗空芯金属红外波导传输的CO2激光施行犬膀胱粘膜剥脱术,通过普通光镜观察、胶原纤维染色及静脉肾盂造影、膀胱压力—容量测定、血清肌酐检测等形态与功能评定的方法了解CO2激光对犬膀胱粘膜的剥脱效果、术后膀胱粘膜的再生、修复过程,以及泌尿系统机能的整体变化。结果:CO2激光可以在10~15min内实现对犬膀胱粘膜的完全剥脱,剥脱深度仅限于粘膜及粘膜下层,未见激光对膀胱肌层有明显的损害。主要并发症为程度不等的终末肉眼血尿,未见有严重膀胱出血、穿孔及尿漏的发生。术后4周时可见膀胱粘膜上皮完全再生,术后12周时膀胱及上尿路的形态与功能方面的各项指标与术前无明显差异,膀胱肌层未见有严重的纤维化改变。结论:CO2激光可以对犬膀胱粘膜进行有效地剥脱,CO2激光犬膀胱粘膜剥脱术具有一定可行性与安全性。     

Polyoxometalate‐Derived Hexagonal Molybdenum Nitrides (MXenes) Supported by Boron,Nitrogen Codoped Carbon Nanotubes for Efficient Electrochemical Hydrogen Evolution from Seawater

MXenes and doped carbon nanotubes (CNTs) have entered into research arenas for high‐rate energy storage and conversion. Herein, a method of postsynthesis of MXenes in boron, nitrogen codoped CNTs (BNCNTs) is reported with their electrocatalytical hydrogen evolution performance. The encapsulation of hexagonal molybdenum nitrate nanoparticles (h‐MoN NPs) into BNCNTs protects h‐MoN NPs from agglomeration and poisoning in the complex environment. In principle, the synergism of B and N dopants on the doped CNTs and confined h‐MoN NPs produces extremely active sites for electrochemical hydrogen evolution. Density functional theory calculations reveal that the active sites for hydrogen evolution originate from the synergistic effect of h‐MoN(001)/CN (graphitic N doping) and h‐MoN(001)/BNC. The h‐MoN@BNCNT electrocatalyst exhibits a small overpotential of 78 mV at 10 mA cm^?2 and Tafel slope of 46 mV per decade, which are dramatically improved over all reported MoN‐based materials and doped CNTs. Additionally, it also exhibits outstanding electrochemical stability in environments with various pH values and seawater media from South China Sea.     

Engineering the Pore Structure and Functionality of Ionic Porous Polymers for Separating Acetylene over Carbon Dioxide

Precise engineering of organic porous polymers to realize the selective separation of structurally similar gases presents a great challenge. In this study, a new class of ionic porous polymers P(Ph3Im-Br-nDVB) with a high ionic density and microporous surface area are constructed through a facile copolymerization strategy, providing an efficient path to rational control over pore structure and functionality. The first example of ionic porous organic polymers is reported to address the challenge of discriminating the subtle difference of C₂H₂ and CO₂, which have almost identical molecular sizes and similar physicochemical properties, which achieve the highest C₂H₂/CO₂ selectivity (17.9) among porous organic polymers. These ionic porous polymers exhibit high stability and excellent dynamic breakthrough performance for binary C₂H₂/CO₂ mixtures, indicating their practical feasibility. Modeling studies reveal that anions are the specific binding sites for preferential C₂H₂ capture because of Br⁻···HCCH interactions. This study not only demonstrates an efficient strategy to build novel ionic porous polymers integrating abundant micropores and ionic sites but also sheds some light on the development of functionalized materials for the separation of structurally similar gas molecules.     

In Situ Synthesis of Molybdenum Carbide Nanoparticles Incorporated into Laser-Patterned Nitrogen-Doped Carbon for Room Temperature VOC Sensing

Carbon laser-patterning (CLaP) is emerging as a new tool for the precise and selective synthesis of functional carbon-based materials for on-chip applications. The aim of this work is to demonstrate the applicability of laser-patterned nitrogen-doped carbon (LP-NC) for resistive gas-sensing applications. Films of pre-carbonized organic nanoparticles on polyethylenetherephthalate are carbonized with a CO₂-laser. Upon laser-irradiation a compositional and morphological gradient in the films is generated with a carbon content of 92% near the top surface. The specific surface areas of the LP-NC are increased by introducing sodium iodide (NaI) as a porogen. Electronic conductivity and surface area measurements corroborate the deeper penetration of the laser-energy into the film in the presence of NaI. Furthermore, impregnation of LP-NC with MoC_1−x (<10 nm) nanoparticles is achieved by addition of ammonium heptamolybdate into the precursor film. The resulting doping-sensitive nano-grain boundaries between p-type carbon and metallic MoC_1−x lead to an improvement of the volatile organic compounds sensing response of ΔR/R₀ = −3.7% or −0.8% for 1250 ppm acetone or 900 ppm toluene at room temperature, respectively, which is competitive with carbon-based sensor materials. Further advances in sensitivity and in situ functionalization are expected to make CLaP a useful method for printing selective sensor arrays.     

空调房间室内CO2浓度实验研究

鉴于室内空气品质的要求,建立室内CO2浓度对比实验,分析造成夏季空调房间室内CO2浓度累积的影响因素,并分析消除室内CO2浓度累积的通风换气量,指出较小的室内人员密度和良好的通风换气是提高室内空气品质的有效保证。     

CuCr合金催化剂制备条件对大电流CNTs阴极的影响

通过改变溅射功率以磁控溅射法制备了Cu/Cr合金催化剂,研究了化学气相沉积法制备的碳纳米管(CNTs)作为大电流密度场发射阴极的场发射性能。采用扫描电镜和场发射测试仪分别对不同功率催化剂制备的CNTs进行了形貌及性能分析。结果表明,根据溅射功率与催化剂颗粒的关系,可以通过调节溅射功率改变CNTs的长径比及密度,在250WCu/Cr催化剂制备的CNTs薄膜具备了良好的场发射性能,阴极电子发射的开启电场仅为1.47V/μm,当电场为3.23V/μm,发射电流密度可高达3259μA/cm2。     

Deciphering Electrolyte Selection for Electrochemical Reduction of Carbon Dioxide and Nitrogen to High-Value-Added Chemicals

Electrochemical reduction of CO₂ (CO₂RR) and nitrogen (NRR) constitute alternatives to fossil fuel-based technologies for the production of high-value-added chemicals. Yet their practical application is still hampered by the low energy and Faradaic efficiencies although numerous efforts have been paid to overcome the fatal shortcomings. To date, most studies have focused on designing and developing advanced electrocatalysts, while the understanding of electrolyte, which would significantly influence the reaction microenvironment, are still not enough to provide insight to construct highly active and selective electrochemical systems. Here, a comprehensive review of the different electrolytes participating in the CO₂RR and NRR is provided, including acidic, neutral, alkaline, and water-in-salt electrolyte as aqueous electrolytes, as well as organic electrolyte, ionic-liquids electrolyte, and the mixture of the two as non-aqueous electrolytes. Through the discussion of the roles of these various electrolytes, it is aimed to grasp their essential function during the electrochemical process and how these functions can be used as design parameters for improving electrocatalytic performance. Finally, priorities for future studies are suggested to support the in-depth understanding of the electrolyte effects and thus guide efficient selection for next-generation gas-involving electrochemical reactions.     

Covalent Functionalization of Multi‐walled Carbon Nanotubes with a Gadolinium Chelate for Efficient T1‐Weighted Magnetic Resonance Imaging

Given the promise of carbon nanotubes (CNTs) for photothermal therapy, drug delivery, tissue engineering, and gene therapy, there is a need for non‐invasive imaging methods to monitor CNT distribution and fate in the body. In this study, non‐ionizing whole‐body high field magnetic resonance imaging (MRI) is used to follow the distribution of water‐dispersible non‐toxic functionalized CNTs administrated intravenously to mice. Oxidized CNTs are endowed with positive MRI contrast properties by covalent functionalization with the chelating ligand diethylenetriaminepentaacetic dianhydride (DTPA), followed by chelation to Gd³⁺. The structural and magnetic properties, MR relaxivities, cellular uptake, and application for MRI cell imaging of Gd‐CNTs in comparison to the precursor oxidized CNTs are evaluated. Despite the intrinsic T₂ contrast of oxidized CNTs internalized in macrophages, the anchoring of paramagnetic gadolinium onto the nanotube sidewall allows efficient T₁ contrast and MR signal enhancement, which is preserved after CNT internalization by cells. Hence, due to their high dispersibility, Gd‐CNTs have the potential to produce positive contrast in vivo following injection into the bloodstream. The uptake of Gd‐CNTs in the liver and spleen is assessed using MRI, while rapid renal clearance of extracellular Gd‐CNTs is observed, confirming the evidences of other studies using different imaging modalities.