石墨烯基气凝胶催化还原特性及其应用

石墨烯基气凝胶(GA)是一种内部连通的三维石墨烯宏观体,其在继承了石墨烯良好的化学稳定性和优良催化性能的同时拥有更高的比表面积和导电性。GA由于其优越的性能和独特的结构在催化、能量存储、吸附等领域得到广泛的应用。本文主要从GA催化还原特性展开,综述了具有不同催化性能的石墨烯基气凝胶的制备方法,将其总结归纳分为GA、掺杂型GA、复合型GA以及掺杂复合型GA四种类型,并详细介绍了制备方法对石墨烯基气凝胶催化性能的影响。石墨烯基气凝胶因具有优良的电化学活性和催化特性,在燃料电池、染料敏化太阳能电池、微生物电解池和电化学传感器等领域具有广泛的应用前景。最后对石墨烯基气凝胶在催化领域的应用前景进行分析和展望。     

Recent Advances in the Synthesis and Application of Three-Dimensional Graphene-Based Aerogels

Three-dimensional graphene-based aerogels (3D GAs), combining the intrinsic properties of graphene and 3D porous structure, have attracted increasing research interest in varied fields with potential application. Some related reviews focusing on applications in photoredox catalysis, biomedicine, energy storage, supercapacitor or other single aspect have provided valuable insights into the current status of Gas. However, systematic reviews concentrating on the diverse applications of 3D GAs are still scarce. Herein, we intend to afford a comprehensive summary to the recent progress in the preparation method (template-free and template-directed method) summarized in Preparation Strategies and the application fields (absorbent, anode material, mechanical device, fire-warning material and catalyst) illustrated in Application of 3D GAs with varied morphologies, structures, and properties. Meanwhile, some unsettled issues, existing challenges, and potential opportunities have also been proposed in Future Perspectives to spur further research interest into synthesizing finer 3D GAs and exploring wider and closer practical applications.     

超亲水疏油材料的制备及其油水分离性能

含油污水的随意排放对海洋、沿海周边环境以及人类健康造成了严重的影响。传统的油水分离方法易造成环境二次污染,同时也是对有限资源的一种损耗。因此,如何高效环保地解决含油污水问题具有重要意义。物理过滤/吸附法被认为是一种高效环保的分离方法,基于仿生学原理,许多可用于物理选择性分离的超亲油疏水和超亲水疏油材料被制备出来。超亲油疏水材料易被油污染,重复利用率低;相比之下,超亲水疏油材料具有自清洁性且重复利用率高,在油水分离方面具有广阔的应用前景。根据基底材料的选择不同,本文综述了金属基以及高分子基超亲水疏油材料的研究现状,总结了其优缺点,并对今后超亲水疏油材料的研究方向和重点进行了展望。     

Wrinkled Graphene Monoliths as Superabsorbing Building Blocks for Superhydrophobic and Superhydrophilic Surfaces

Superhydrophobic and superhydrophilic surfaces are of great interest because of a large range of applications, for example, as antifogging and self‐cleaning coatings, as antibiofouling paints for boats, in metal refining, and for water–oil separation. An aqueous ink based on three‐dimensional graphene monoliths (Gr) can be used for constructing both superhydrophobic and superhydrophilic surfaces on arbitrary substrates with different surficial structures from the meso‐ to the macroscale. The surface wettability of a Gr‐coated surface mainly depends on which additional layers (air for a superhydrophobic surface and water for a superhydrophilic surface) are adsorbed on the surface of the graphene sheets. Switching a Gr‐coated surface between being superhydrophobic and superhydrophilic can thus be easily achieved by drying and prewetting with ethanol. The Gr‐based superhydrophobic membranes or films should have great potential as efficient separators for fast and gravity‐driven oil–water separation.     

Catalytic Properties of Mechanically Activated Humic Substances in Electroreduction of Oxygen

Effect of mechanical treatment of peat on the yield of the major fractions (polysaccharides, poly- phenols, water-soluble compounds, and humic acids) and catalytic activity of humic substances in oxidation processes is studied. Conditions of formation of substances with the maximal antioxidant and initiating activities are determined. The antioxidant and initiating activities of the polysaccharide and humic fractions is studied, in relation to the structure and iron content.     

New Carbon Aerogels Fabricated from Polymeric Materials and Their Properties

Electron microscopy and adsorption-structural, X-ray phase, and thermal analyses were used to determine the density, porosity, microstructure, electrical conductivity, and reactivity of new carbon aerogels based on phenol-formaldehyde polymers.     

Superhydrophobic and Conductive Wire Membrane for Enhanced CO2 Electroreduction to Multicarbon Products

Gas-liquid-solid triple-phase interfaces (TPI) are essential for promoting electrochemical CO₂ reduction, but it remains challenging to maximize their efficiency while integrating other desirable properties conducive to electrocatalysis. Herein, we report the elaborate design and fabrication of a superhydrophobic, conductive, and hierarchical wire membrane in which core–shell CuO nanospheres, carbon nanotubes (CNT), and polytetrafluoroethylene (PTFE) are integrated into a wire structure (designated as CuO/F/C(w); F, PTFE; C, CNT; w, wire) to maximize their respective functions. The realized architecture allows almost all CuO nanospheres to be exposed with effective TPI and good contact to conductive CNT, thus increasing the local CO₂ concentration on the CuO surface and enabling fast electron/mass transfer. As a result, the CuO/F/C(w) membrane attains a Faradaic efficiency of 56.8 % and a partial current density of 68.9 mA cm⁻² for multicarbon products at −1.4 V (versus the reversible hydrogen electrode) in the H-type cell, far exceeding 10.1 % and 13.4 mA cm⁻² for bare CuO.     

Catalytic Potential of Post-Transition Metal Doped Graphene-Based Single-Atom Catalysts for the CO2 Electroreduction Reaction

Catalysts are required to ensure electrochemical reduction of CO₂ to fuels proceeds at industrially acceptable rates and yields. As such, highly active and selective catalysts must be developed. Herein, a density functional theory study of p-block element and noble metal doped graphene-based single-atom catalysts in two defect sites for the electrochemical reduction of CO₂ to CO and HCOOH is systematically undertaken. It is found that on all of the systems considered, the thermodynamic product is HCOOH. Pb/C₃, Pb/N₄ and Sn/C₃ are identified as having the lowest overpotential for HCOOH production while Al/C₃, Al/N₄, Au/C₃ and Ga/C₃ are identified as having the potential to form higher order products due to the strength of binding of adsorbed HCOOH.     

超疏水膜的制备及其在膜蒸馏过程中的应用

超疏水材料具有超高的憎水性和自清洁特性,因而在解决材料的润湿和污染方面具有广泛的应用前景。膜蒸馏是一种以多孔疏水膜两侧蒸汽压差为推动力的膜分离过程,是脱盐和水回用中的重要技术。然而膜润湿和污染问题是导致膜蒸馏过程出水品质下降和应用过程稳定性差的关键。本文以膜蒸馏过程为背景,系统介绍了蒸馏过程的发展状况和超疏水膜材料的制备方法,以及超疏水膜在膜蒸馏中的应用,探讨了超疏水膜材料在膜蒸馏过程中的优势,同时指出了其不足和可能的解决方法,以期为膜蒸馏材料的发展提供研究方向和思路。     

Electrical Conductivity of Hydrophobized Electrodes Fabricated from Thermally Expanded Graphite and Their Activity in Electroreduction of Oxygen

Intercalation compounds of GT-1 and GAK-3 graphites were electrically synthesized in concentrated sulfuric and nitric acids. Porous composite samples based on thermally expanded graphite produced from electrochemically synthesized GT-1 graphite hydrosulfate, chemically synthesized GSM-1 graphite nitrate, and fluoroplastic-4D (1–15 wt %), with a volume density of 650–1090 g l^?2, were fabricated and studied.     

Electrocatalytic Activity of Macroheterocyclic Complexes in the Molecular Oxygen Electroreduction: A Cyclic Voltammetry Estimate

Electrochemical and electrocatalytic properties of differently structured macroheterocyclic complexes (MC) are studied by a cyclic voltammetry method. The potential at half-height of the rising branch of the peak current of the first stage in the oxygen reduction, , is used for estimating the electrocatalytic action of complexes. Major structural factors that exert maximum electrocatalytic action on the oxygen reduction are determined by comparing for different MC. The maximum electrocatalytic activity in this reaction in 0.1 M KOH is exhibited by complexes containing cobalt and iron as the central metal atom as well as polymeric compounds and those having electron-donating substituents in the organic ligand.     

Scaling Properties and Structure of Aerogels

Young’s modulus as well as solid thermal and electrical conductivity of aerogels have been observed to scale with density. No quantitative explanations were available up to now for these experimental findings. To establish a quantitive relationship between morphological and topological features of fractal gel networks, a simulation procedure is introduced that allows to produce three-dimensional gel structures, from which two important parameters can be extracted: i) the fraction α of interconnected mass of the gel network and ii) the ratio γ of Pythagorean distance to minimum path length on the gel backbone. Surprisingly the product αγ, which enters important macroscopic parameters such as elasticity or solid thermal (and electrical) conductivity, was found to scale with an exponent that is only a function of the mass fractal dimensionD. Also, an analytical relation between modulus and conductivity can be derived.     

Methanol Tolerant FeTPP—Pt／C Co—catalysts for the Electroreduction of Oxygen

It was found for the first time that iron tetraphenylporphyrin(FeTPP)-Pt/C showed the good activity for the electroreduction of oxygen and methanol tolerant abitity,Their perfor-mances were related to the heat-treatment temperature.     

石墨烯非共价功能化及其应用

石墨烯的湿法化学修饰,主要包括共价及非共价两种,是目前广泛采用的宏量功能化策略,亦是有效避免其团聚而充分发挥其优异纳米性能的重要修饰方法。非共价功能化因可同时保持原有及引入物质的物化性质,并可充分发挥协同作用,近年来已受到比共价修饰更多的研究关注,并已在生物科学与技术、可持续能源储存及转化、医疗和复合材料等诸多领域得到了广泛应用。本文综述了以应用为导向的石墨烯非共价功能化的构建策略,期望文中涉及的湿法组装策略能为进一步构建性能提升的新材料提供参考。     

Synthesis and Photocatalytic Properties of Titanium-Porphyrinic Aerogels

We present novel titanium-porphyrinic gels (TPGs) and titanium-porphyrinic aerogels (TPAs), in which porphyrinic ligand tetrakis(4-carboxyphenyl)porphyrin is coordinated to Ti-oxo clusters. These hierarchically porous TPAs, with micro-, meso-, and macropores and reactant-concentration-dependent Brunauer-Emmett-Teller surface areas of 407–738 m² g⁻¹, are prepared by CO₂ critical point drying of TPGs. Although the Ti⁴⁺ → Ti³⁺ photoreduction of TPAs is less efficient than that of crystalline microporous Ti-porphyrinic framework DGIST-1, prompt diffusion of O₂ and spin-trapping agents into the TPA pores causes the rapid generation of reactive oxygen species (ROS), as observed by EPR spectroscopy. When used as an ROS scavenger, large 1,3-diphenylisobenzofuran is degraded by the best-performing TPA 10 times faster than by DGIST-1, suggesting that the accessibility of molecules (reactants) to pores (reactive centers) strongly influences photocatalytic activity.     

Synthesis of Crosslinked Polymeric Particles and Their Application for the Superhydrophobic Surfaces Using Structured Polymeric Colloids

In this study, structured colloids such as self-organized supraparticles of polymeric lattices were used as coating materials for the fabrication of superhydrophobic surfaces. Crosslinked polystyrene (PS) nanospheres were synthesized using divinylbenzene as crosslinker to prevent the organic particles from being dissolved in toluene solvent. After evaporation-driven self-assembly of PS particles inside the toluene emulsions, supraparticles of PS lattices were fabricated and coated on glass substrate, followed by the plasma treatment using CHF₃ as gas source for fluorination process. After the fluorine treatment using plasma, superhydrophobicity was assessed by measuring water contact angle. The morphologies of supraparticles and the structure of coating film were observed using scanning electron microscope, and the elemental compositions of the coating films were detected by using X-ray photoemission spectroscopy (XPS) technique. We believe that the lotus effect from the supraparticles with different two length scales made crucial contribution to the generation of superhydrophobicity after plasma treatment for the formation of superhydrophobic surfaces.     

Hierarchical Pore Structures Fabricated by Electron Irradiation of Silicone Grease and their Applications to Superhydrophobic and Superhydrophilic Films

Unique hierarchical pore structures were fabricated by simply irradiating an electron beam onto silicone grease films. The hierarchical pore structures consisted of micrometer‐sized pores and macroporous walls. Due to the high surface roughness, the hierarchical pore structures exhibited both superhydrophobicity with a water contact angle (CA) of 170° and superhydrophilicity with an extremely low water CA of 3° after the chemical treatment of the surfaces. In addition to the hierarchical pore structures, sponge‐like pore structures were also fabricated by the electron irradiation of silicone grease films.

     

金属表面分子纳米结构的构筑及性质研究

结合近期研究工作, 简要介绍了在溶液环境下, 利用有机分子在金属表面构筑纳米结构, 利用光化学反应方法调控所得的纳米结构, 利用电化学扫描隧道显微镜对这些结构进行观察, 及利用毛细管隧道结方法测量纳米结构电学性质的相关结果. 并展望了表面纳米结构的构筑、控制和性质研究领域的发展趋势.     

模板辅助合成氮掺杂的多孔碳基氧还原电催化剂的研究进展

氮掺杂的多孔碳材料有望能取代当前普遍应用于质子交换膜燃料电池和金属-空气电池阴极中的贵金属氧还原催化剂,因而备受关注. 模板辅助合成技术作为一种可靠、通用的方法已经在多孔碳电催化剂的制备中得到了广泛的应用. 在碳基ORR电催化剂中,其ORR活性受到诸多因素的影响,如掺杂剂的浓度及其在碳上的分子掺杂态、孔洞结构、比表面积以及碳基材料的导电性等. 本文对近期氮掺杂多孔碳电催化剂的设计、制备、功能化及其在氧还原电催化中的应用研究进展进行了总结,同时展望了模板辅助合成法的一些发展趋势.     

三维石墨烯基材料的制备、结构与性能

石墨烯具有单层碳原子组成的六方晶系晶体结构及独特的电学、化学、力学和热学性质。然而,由于石墨烯片层之间较强的π-π键和范德华力,导致易团聚或堆积,使其比表面积大幅减小,严重损害其性能。解决上述问题的最有效方法之一是构建具有多孔结构的三维石墨烯基材料,不仅保留了石墨烯优秀的导电性能和力学性能等本征特性,而且获得密度低、比表面积大、孔隙率高等结构优点,进而满足吸附剂、催化剂载体、生物传感器及电池与超级电容器电极材料等先进功能材料领域的应用需要。因此,开发三维石墨烯基材料的先进制备方法成为本领域研究的热点方向。本文综述了三维石墨烯基材料的现有制备方法,包括自组装法(水热还原法、化学还原法及冷冻干燥法)、模板法(胶体模板法、模板辅助化学气相沉积法及模板辅助水热还原法)和3D打印法(直写成型法、喷墨打印法、熔融沉积成型法、光固化成型法、选区激光烧结法及选区激光熔融法),总结了上述方法的优点及当前存在的主要问题,并且对三维石墨烯基材料制备技术的发展方向进行了展望。