超薄钯铜纳米片组装纳米花的构建及其氧还原性能

在原子水平上精确调控电催化剂的组成是增强其氧还原（ORR）性能的有效途径。本文采用简单的一步溶剂热还原法制备了由不同PdCu组成的超薄双金属纳米片自组装而成的三维（3D）合金纳米花（Pd₁Cu_x NCFs）。利用透射电子显微镜（TEM）、扫描透射电子显微镜-能谱仪（STEM-EDS）、X射线粉末衍射（XRD）和X射线光电子能谱（XPS）等手段系统表征了Pd₁Cu_x NCFs的形貌、晶体结构及成分。相比于传统二维（2D）纳米材料,Pd₁Cu_x NCFs丰富的快速传质路径、较高的Pd原子利用效率和更强的PdCu双金属间协同作用使得其在碱性介质中表现出增强的ORR性能。另外,本文还研究了Pd、Cu前体用量对ORR性能的影响。结果显示,Pd、Cu前体摩尔比为1∶0.5时,催化剂（Pd₁Cu_0.5NCFs）在碱性介质中ORR活性和电化学稳定性最佳。其半波电位E_1/2（0.937V）远高于商业Pt/C（0.851V）;在加速循环1000次扫描后,E_1/2几乎没有变化,说明其稳定性优异;0.90V电势下,Pd₁Cu_0.5 NCFs的质量比活性为1.09A/mg,是商业Pt/C的14.5倍。     

N-doped hierarchically macro/mesoporous carbon with excellent electrocatalytic activity and durability for oxygen reduction reaction

A novel kind of N-doped hierarchically porous carbon materials (HPC-Ns) has been successfully synthesized with hierarchically macro/mesoporous silica as a hard template followed by a simple N-doping procedure using low-cost and nontoxic urea as the nitrogen source. The synthesized HPC-N samples demonstrated extensive three-dimensional (3D) connected macroporosity and partially ordered mesoporosity, extremely large specific surface area, favorable graphitization degree, and high relative content of pyridinic N, which is active to the oxygen reduction reaction (ORR). Due to the combined contributions of the above features, the metal-free HPC-Ns demonstrated excellent performance in ORR with a highly comparable limiting current density but much higher current output stability and resistance towards the fuel crossover effect compared to the commercial Pt/C, as well as the dominant 4 e⁻ reduction mechanism. Thus, it is believed that HPC-N has the potential to be used in polymer electrolyte membrane fuel cells.     

Hierarchically porous N-doped carbon nanoflakes: Large-scale facile synthesis and application as an oxygen reduction reaction electrocatalyst with high activity

Hierarchically porous N-doped carbon nanoflakes (HPNCNFs) were facilely synthesized on a large scale via pyrolysis of 1,8-diaminonaphthalene (DAN)/FeCl₃·6H₂O mixture under Ar followed by acid leaching. Both pyrolysis temperature and the amount of Fe species have strong influence on catalyst activity. It suggests that the presence of large excess Fe species not only is key to nanoflake formation but also serves as a mesopore-forming agent. The HPNCNF-900 catalyst, obtained at 900 °C with a mass ratio 1:5 of DAN to FeCl₃·6H₂O, was found to exhibit superhigh oxygen reduction reaction activity and excellent durability in alkaline media outperforming the state-of-the-art Pt/C catalyst at a moderate loading.     

Nitrogen-doped carbon coated palygorskite as an efficient electrocatalyst support for oxygen reduction reaction

An electrocatalyst support, nitrogen-doped graphitic layer (CN_x) coated palygorskite (PLS) (donated as PLS@CN_x), is synthesized by carbonizing the polypyrrole (PPy) coated PLS and is explored for the first time as a cathode electrocatalyst support in proton exchange membrane fuel cell. The structural and chemical properties of the PLS@CN_x are investigated by Fourier-Transform infrared spectrometer, thermogravimetric analysis, X-ray diffraction and transmission electron microscopy. The electrocatalytic activity and stability of Pt/PLS@CN_x toward oxygen reduction reaction (ORR) are studied by cyclic voltammetry (CV) and steady state polarization measurements. Upon loading Pt (20 wt%), the catalysts exhibit superior catalytic performance during ORR, surpassing the conventional Pt/C (Vulcan XC-72) catalysts. High electrocatalytic activity and good stability can be attributed to the nitrogen atom incorporation and SiO₂ component in PLS.     

Multivalent manganese oxides with high electrocatalytic activity for oxygen reduction reaction

A noble-metal-free catalyst based on both Mn₃O₄ and MnO was prepared by using the dielectric barrier discharge technique at moderate temperature. The prepared catalyst shows a higher electrocatalytic activity towards the oxygen reduction reaction than the catalyst prepared by using the traditional calcination process. The enhanced activity could be due to the coexistence of manganese ions with different valences, the higher oxygen adsorption capacity, and the suppressed aggregation of the catalyst nanoparticles at moderate temperature. The present work would open a new way to prepare low-cost and noble-metal-free catalysts at moderate temperature for more efficient electrocatalysis.

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Effects of pore structure in nitrogen functionalized mesoporous carbon on oxygen reduction reaction activity of platinum nanoparticles

Nitrogen-doped mesoporous carbons (NMCs) with ordered to disordered pore structures were fabricated on SBA-15 modified with different concentrations of tetraethyl orthosilicate using pyrrole as a carbon source. The carbonization temperature of NMCs was maintained at 800 °C so that the amount and type of nitrogen functionalities were constant. Pt nanoparticles (NPs) were deposited onto NMCs using a modified polyol process. N₂ adsorption isotherms, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy were used to characterize NMCs and Pt NPs. A significant shift in binding energy was found in Pt NPs deposited on NMC with disordered pore structure compared to Pt NPs deposited on NMC with ordered pore structure. Pt NPs deposited on NMC with the disordered pore structure had the highest intrinsic oxygen reduction reaction (ORR) activity among the Pt/NMC catalysts. It showed that the interaction between Pt NPs and NMCs could be modulated for enhancement of the ORR activity of Pt NPs by changing the pore structure of NMCs.     

双介孔炭制备及应用研究进展

双介孔炭材料具有两种不同的介孔孔径,可以满足不同直径分子的传输需要,并且具有惰性的材料表面,有利于改性,因此日益受到研究者的广泛关注.本文较为详尽地介绍了目前双介孔炭材料的制备方法及应用现状,指出有效控制孔结构、孔径分布及进一步开发双介孔炭材料的应用是未来研究的主要方向.     

Modified porous carbon materials as catalytic support for cathodic reduction of dioxygen

Activated carbon materials were modified by generating several functional groups containing oxygen and/or nitrogen atoms on their surfaces. Surface properties of obtained carbon samples were investigated. The point of zero charge was determined by different methods. The catalytic properties of these materials in the decomposition of hydrogen peroxide and in the electrochemical reduction of dioxygen in aqueous electrolytes have been studied. The catalytic activity for O₂ reduction correlates with that for HO₂⁻ decomposition. A linear relationship was derived for the dioxygen reduction peak potential and the decomposition rate constant. Thus, the selection of active catalysts for the heterogeneous decomposition of HO₂⁻ is a good starting point for the design of a carbon-based oxygen cathode.     

氧化硅气凝胶绝热材料及其建筑减碳应用

无机氧化硅气凝胶因具有超低导热系数、A级不燃、吸湿率低、轻质等特点,在航天航空、工业及建筑领域的节能减碳方面具有广泛的应用潜力。然而氧化硅气凝胶力学性能差、制备成本高等缺点限制了其发展应用。介绍了氧化硅气凝胶绝热材料制备工艺的研究进展,对氧化硅气凝胶在建筑领域的应用形式（如超轻气凝胶泡沫混凝土、超高性能气凝胶保温隔热板、超低传热系数气凝胶节能玻璃等）进行了综述,并对氧化硅气凝胶在建筑节能领域的发展方向进行了展望。响应碳中和发展目标,随着气凝胶制备技术的发展与成本降低,氧化硅气凝胶绝热材料将在建筑墙体保温隔热方面广泛应用,同时对其性能提出了更多功能性要求,对氧化硅气凝胶材料还需开展更系统的基础研究以及工程应用技术研发,推动建筑领域的节能减碳与可持续发展。     

Electrocatalytic activity of nitrogen doped carbon nanotubes with different morphologies for oxygen reduction reaction

Nitrogen doped carbon nanotubes (NCNTs) were synthesized by a single step chemical vapor deposition technique using either ferrocene or iron(II) phthalocyanine as catalyst and pyridine as the carbon and nitrogen precursor. Variations in surface morphology and electrocatalytic activity for oxygen reduction reaction (ORR) were observed between the NCNTs synthesized using different catalysts. The structural and chemical characterizations were carried out using transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The electrochemical activity of NCNTs was evaluated with rotating ring disc electrode (RRDE) voltammetry. Structural characterization suggested more defects formed on the NCNTs synthesized from ferrocene (Fc-NCNTs) which led to a rugged surface morphology compared to the NCNTs synthesized from iron(II) phthalocyanine (FePc-NCNTs). Based on the RRDE voltammetry study, Fc-NCNTs demonstrated much higher activity for ORR than FePc-NCNT. Evidences from the structural and chemical characterizations illustrate the potential impact of catalyst structure in shaping the surface structure of NCNTs and the positive effect of surface defects on ORR activity. These results showed that potential improvements on ORR activity of NCNTs could be achieved by tailoring the surface structure of NCNTs by using catalysts with different structures.     

掺氮碳纳米管的结构、制备及其催化应用

将氮原子掺入到碳纳米管的晶格中,使碳纳米管表面碱性增强,从而改变了碳纳米管表面的吸附性能;掺杂在碳纳米管晶格中的氮原子的高电子云密度还导致碳纳米管在电子、材料和催化方面具有独特的性能.介绍了掺氮碳纳米管结构特征和制备方法,综述了近年来在催化中的应用.     

氮杂化介孔碳制备方法及在超级电容器中的应用进展

氮杂化介孔碳是在有序介孔碳的骨架中掺入氮原子部分取代碳原子形成的多孔物质,是一种具有优异性价比的新型碳材料。综述了氮杂化介孔碳的各种制备方法及其特点,重点介绍了混合聚合物炭化法和共聚物炭化活化结合法等新型的氮杂化介孔碳的制备方法;介绍了制备氮杂化介孔碳的碳、氮原料的来源和特点;总结并提出了提高氮杂化介孔碳比电容的途径和方法;提出了导电性氮杂化介孔碳的制备新方法。建议将氮杂化介孔碳的制备和酚类废物处理结合起来,以实现酚类废物的综合利用;建议将掺氟氧化锡原位引入氮杂化介孔碳的制备中,催化活化得到导电性氮杂化介孔碳材料。     

Synthesis and characterization of mesoporous Mn/Al-SBA-15 and its catalytic activity for NO reduction with ammonia

Al-SBA-15 was prepared by one-step hydrothermal synthesis method, and was characterized by X-ray diffraction, N₂-adsorption, transmission electron microscope and Fourier infrared spectra of chemisorbed pyridine (Py-IR). The results showed that Al-SBA-15 had well-ordered hexagonal mesopores. As compared with Si-SBA-15, Al-SBA-15 had thicker pore wall, higher surface area, and stronger Lewis acidity. Due to the stronger Lewis acidity, Mn/Al-SBA-15 catalyst prepared by impregnation showed better activity than Mn/Si-SBA-15 in the selective catalytic reduction of NO by NH₃.     

The particle size effect of N-doped mesoporous carbons as oxygen reduction reaction catalysts for PEMFC

The particle size effect of N-doped mesoporous carbon was investigated for ORR activity in acid condition and for issue of a mass transfer and gas diffusion in PEMFCs. As for a non-Pt ORR catalyst, nitrogen (N)-doped ordered mesoporous carbons (OMCs) with a various particle sizes with the range of the average 20, 45 and 75 μm were synthesized by the precursor of polyaniline for the N/C species, and a mesoporous silica template was used for the physical structure for preparation of nitrogen doped OMCs. The N-doped mesoporous carbons are promoted by a transition metal (Fe) to improve catalytic activity for ORR in PEMFCs. All the prepared carbons were characterized by via scanning electron microscopy (SEM), and to evaluate the activities of synthesized doped carbons, linear sweep was recorded in an acidic solution to compare the ORR catalytic activities values for the use in the PEMFC system. The surface area and pore volume were increased as the particles decreased, which was effective for the mass transfer of the reactant for higher activity at the limiting current regions.     

Uniform nitrogen and sulfur co-doped carbon nanospheres as catalysts for the oxygen reduction reaction

Uniform nitrogen and sulfur co-doped carbon nanospheres with an average diameter of approximately 200 nm were prepared using sulfur and polyacrylonitrile as precursors. The materials were characterized using scanning electron microscopy, transmission electron microscopy, elemental analysis, and X-ray photoelectron spectroscopy. The characterization results suggest the as-prepared materials had uniform, porous, nanospherical morphologies and high surface areas. For the typical sample containing 9.5% sulfur, the surface area is up to 653 m² g⁻¹. The catalysts exhibited enhanced catalytic activity, outstanding long-term stability, and excellent methanol tolerance in an alkaline medium. Significantly, the sulfur addition was found to be vital in improving materials’ catalytic performance through preventing aggregation of the nanospheres, constructing porous structures, increasing the surface area, and participating in the formation of active sites.     

Nitrogen/sulfur dual-doped mesoporous carbon with controllable morphology as a catalyst support for the methanol oxidation reaction

Ordered mesoporous carbon (OMC) was synthesized by nano-casting method using novel fluidic precursor – acrylonitrile telomer (ANT). By the penetration of mesoporous silica template with pure ANT, followed by the stabilization, carbonization and removal of the template, we obtained highly ordered mesoporous carbon rods (specific area 408 m² g⁻¹). When an acetone solution of ANT (66 and 33 wt.%) was used instead of pure ANT, carbon materials with mesopore ranging from 2 to 7 nm were obtained (specific area 843 and 1012 m² g⁻¹ respectively). Both nitrogen and sulfur atoms were doped into mesoporous carbon with 4 and 0.6 at.% using nitrogen containing monomer and sulfur containing chain transfer agent, without involving complicated synthetic technique and poisonous gaseous compounds. This method was proved to be a facile way to synthesize nitrogen and sulfur containing OMC with partially controllable pore distribution and morphology. More importantly, due to unique mesopore structure and heteroatom doping, Pt nano-particles deposited on the OMCs showed electrocatalytic activity as high as 508 mA mg⁻¹ Pt in methanol oxidation which is 1.7-fold of activity of Pt deposited on commercial Vulcan carbon black.     

Carbon nanocapsules as an electrocatalyst support for the oxygen reduction reaction in alkaline electrolyte

Carbon Nanocapsules (CNCs) were investigated for their electrocatalytic performances for the oxygen reduction reaction in alkaline electrolyte. With an average diameter of 10–30 nm, the CNCs are composed of graphene layers encapsulating a hollow core. A gas diffusion electrode (GDE) made of CNCs revealed a much enhanced i–V polarization response than that of Vulcan XC72. However, its performance was moderately lower than that of Black Pearls 2000. In addition, the CNCs were impregnated with nanoparticles of Ag, MnO _x and CoO _x . The i–V and galvanostatic results of the catalyzed CNCs indicated significant improvements over that of noncatalyzed CNCs. For example, a Ag–CNC derived GDE was capable of delivering 1.03 and 0.88 V at current densities of 100 and 200 mA cm⁻², respectively. Our study offers direct evidence that the CNCs not only exhibit unique electrocatalytic abilities but also function superbly as an electrocatalyst support.