钴,氮共掺杂多孔炭用于高性能氧还原电催化剂

钴和氮共掺杂炭催化剂(Co-NC),由于成本低廉和资源丰富而备受关注,但其低的氧还原反应(ORR)活性和对氧气的双电子(2e-)还原生成H2O2的高选择性,进一步影响了其在燃料电池中的应用.因此,Co-NC催化剂是通过在650、750和850℃下热解CoCl2和壳聚糖的混合物(用ZnCl2预处理),然后用HNO3洗涤并...     

杂原子掺杂碳材料用于氧还原反应催化剂的研究

氧还原反应存在于多种储能设备如空气电池和燃料电池的反应过程中,通常以商业铂碳作为催化剂,但铂基催化剂的高昂价格和易中毒的缺点限制了其广泛应用.碳基材料被认为是贵金属催化剂最有希望的替代物,引起了众多研究者的兴趣.这是因为某些杂原子掺杂于碳基体中会因为其与碳原子的物理化学性质的差异而在基体中形成缺陷,形成催化的活性位点,...     

铁氮共掺杂介孔碳材料的简易制备及其氧还原反应催化性能

氧还原反应(ORR)是燃料电池阴极重要的电化学反应过程,其自发反应进程缓慢,对氧还原反应起高效催化作用的催化剂面临价格昂贵、合成流程复杂、污染环境等问题,因此探索合成简单、环境友好的氧还原催化剂制备方法具有重要意义。铁氮共掺杂介孔碳材料(Fe-N/MC)是一种有巨大应用价值的非贵金属氧还原反应催化剂。本工作通过在马弗炉中的半封闭体系内高温碳化小分子前驱体得到介孔碳材料(MC_M),再把获得的MC_M与铁盐混合在管式炉中高温处理制备得到铁氮共掺杂介孔碳材料(Fe-N/MC_MT)。该方法热解条件简单,无需模板剂和NH₃、HF等有毒物质。由于MC_M含有较高的氮和氧元素,有利于提升介孔碳材料表面的亲水性和配位能力,通过MC_M和铁盐制备出的Fe-N/MC_MT含有丰富的、催化ORR的Fe-N_x活性位点,其起始电位和半波电位分别为0.941和0.831 V(vs RHE),比商业化Pt/C催化剂的起始电位和半波电位分别正34和16...     

氮硫共掺杂碳材料均匀担载核壳纳米颗粒Co@Co9S8作为氧还原催化剂的研究

开发高效、稳定的非贵金属氧还原(ORR)催化剂是促进燃料电池商业化进程的关键。通过树脂衍生N、S共掺杂碳材料负载原位生成的Co@Co₉S₈核壳结构纳米颗粒,制备出一种具有良好活性和稳定的非贵金属催化剂Co@Co₉S₈/NSC。电化学测试结果表明：Co@Co₉S₈/NSC催化剂的半波电位(E_1/2)和极限电流密度可与商业Pt/C催化剂相媲美。同时相较商业Pt/C催化剂,其还具有极好的抗甲醇活性。此外,计时电流测试表明：持续老化10000s后,Co@Co₉S₈/NSC的电流密度保持了初始值的97.5%,远低于商业Pt/C催化剂的23.3%。为构建高活性高稳定性核壳结构ORR催化剂提供了新的思路,同时其思路也可以应用于其他新能源电极材料如Li-空气电池、Li-S电池及超级电容器等。     

自组装合成金属-氮共掺杂多孔碳球及电催化氧还原性能研究

通过无模板自组装法与自牺牲制孔方式相结合,制备金属-氮(M-N)原位共掺杂的多孔碳球材料(M/N-CS,M=Cu、Fe或Ni)。该方法通过二苯碳酰二肼、金属离子与糠醛自组装形成聚合物球,在碳化过程中球体中不稳定的含氮微区分解形成多孔结构,同时原位形成具有高催化活性的M-N_X活性位点。通过控制金属源和多重反应条件,既能保证碳化阶段碳球结构的稳定,又可实现材料的孔隙率、孔径及形貌的灵活变化。利用SEM、TEM、XRD、物理吸附及XPS测试分别对材料的结构和掺杂进行分析。所得材料用于电催化氧还原测试,其中Fe/N-CS材料的催化反应初始电位和半波电位分别为0.91V和0.79V(vs.RHE),并以4e^-转移方式进行反应。同时,催化材料表现出远高于商业Pt/C催化剂的稳定性与耐甲醇性。     

碳热还原-反应烧结法制备多孔氮化硅陶瓷

以廉价的二氧化硅、炭黑和硅粉为起始原料, 利用碳热还原-反应烧结法制备了高气孔率、孔结构均匀的多孔氮化硅陶瓷, 考察了原料中硅粉含量对多孔氮化硅陶瓷微观组织和力学性能的影响。XRD分析表明烧结后的试样成分除了少量的α-Si₃N₄相和晶间相Y₂Si₃O₃N₄外, 其余都是β-Si₃N₄相; SEM分析显示微观组织由棒状β-Si₃N₄晶粒和均匀的孔组成。通过改变硅粉的含量, 制备了不同气孔率, 力学性能优异的多孔氮化硅陶瓷。     

金属和非金属共掺杂TiO_2催化剂光催化活性研究

采用溶胶-凝胶法制备了B、N和Ce共掺杂TiO2光催化剂,并用XRD、SEM等表征了其结构特征。以酸性大红染料为模型化合物,探索了其光催化性能,同时考察了制备条件对共掺杂TiO2催化剂活性的影响。结果表明,当B、N和Ce的原子为1∶2∶0.1时,光催化剂活性最大,大红染料的降解率达到98%。     

生物质多孔碳的制备、掺杂及应用

生物质多孔碳是一种绿色、廉价、来源广泛、理化性质易于调控的可再生能源,在能源与环境修复等领域具有广泛的应用潜力和前景。主要介绍了目前常用于制备生物质多孔碳材料的主要方法、活化方法以及掺杂方法。在此基础上,综述了生物质多孔碳材料在多相催化、超级电容器、吸附、电极材料以及微波吸收等方面的研究进展,并对未来的发展趋势进展了总结和展望。     

Rational design of hierarchically porous Fe-N-doped carbon as efficient electrocatalyst for oxygen reduction reaction and Zn-air batteries

The rational design and construction of hierarchically porous nanostructure for oxygen reduction reaction (ORR) electrocatalysts is crucial to facilitate the exposure of accessible active sites and promote the mass/electron transfer under the gas-solid-liquid triple-phase condition. Herein, an ingenious method through the pyrolysis of creative polyvinylimidazole coordination with Zn/Fe salt precursors is developed to fabricate hierarchically porous Fe-N-doped carbon framework as efficient ORR electrocatalyst. The volatilization of Zn species combined with the nanoscale Kirkendall effect of Fe dopants during the pyrolysis build the hierarchical micro-, meso-, and macroporous nanostructure with a high specific surface area (1,586 m²·g⁻¹), which provide sufficient exposed active sites and multiscale mass/charge transport channels. The optimized electrocatalyst exhibits superior ORR activity and robust stability in both alkaline and acidic electrolytes. The Zn-air battery fabricated by such attractive electrocatalyst as air cathode displays a higher peak power density than that of Pt/C-based Zn-air battery, suggesting the great potential of this electrocatalyst for Zn-air batteries.

     

Natural tea-leaf-derived,ternary-doped 3D porous carbon as a high-performance electrocatalyst for the oxygen reduction reaction

To commercialize fuel cells and metal-air batteries, cost-effective, highly active catalysts for the oxygen reduction reaction (ORR) must be developed. Herein, we describe the development of low-cost, heteroatom (N, P, Fe) ternary-doped, porous carbons (HDPC). These materials are prepared by one-step pyrolysis of natural tea leaves treated with an iron salt, without any chemical and physical activation. The natural structure of the tea leaves provide a 3D hierarchical porous structure after carbonization. Moreover, heteroatom containing organic compounds in tea leaves act as precursors to functionalize the resultant carbon frameworks. In addition, we found that the polyphenols present in tea leaves act as ligands, reacting with Fe ions to form coordination compounds; these complexes acted as the precursors for Fe and N active sites. After pyrolysis, the as-prepared HDPC electrocatalysts, especially HDPC-800 (pyrolyzed at 800 °C), had more positive onsets, half-wave potentials, and higher catalytic activities for the ORR, which proceeds via a direct four-electron reaction pathway in alkaline media, similar to commercial Pt/C catalysts. Furthermore, HDPC-X also showed enhanced durability and better tolerance to methanol crossover and CO poisoning effects in comparison to commercial Pt/C, making them promising alternatives for state-of-the-art ORR electrocatalysts for electrochemical energy conversion. The method used here provides valuable guidelines for the design of high-performance ORR electrocatalysts from natural sources at the industrial scale.

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An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes

Oxygen reduction reaction catalysts based on precious metals such as platinum or its alloys are routinely used in fuel cells because of their high activity. Carbon-supported materials containing metals such as iron or cobalt as well as nitrogen impurities have been proposed to increase scalability and reduce costs, but these alternatives usually suffer from low activity and/or gradual deactivation during use. Here, we show that few-walled carbon nanotubes, following outer wall exfoliation via oxidation and high-temperature reaction with ammonia, can act as an oxygen reduction reaction electrocatalyst in both acidic and alkaline solutions. Under a unique oxidation condition, the outer walls of the few-walled carbon nanotubes are partially unzipped, creating nanoscale sheets of graphene attached to the inner tubes. The graphene sheets contain extremely small amounts of irons originated from nanotube growth seeds, and nitrogen impurities, which facilitate the formation of catalytic sites and boost the activity of the catalyst, as revealed by atomic-scale microscopy and electron energy loss spectroscopy. Whereas the graphene sheets formed from the unzipped part of the outer wall of the nanotubes are responsible for the catalytic activity, the inner walls remain intact and retain their electrical conductivity, which facilitates charge transport during electrocatalysis.     

One-step synthesis of N,P co-doped porous carbon electrocatalyst for highly efficient nitrogen fixation

Heteroatom-doped porous carbon has attracted many researchers'interests owing to their hierarchical porous and more active sites for nitrogen reduction reaction...     

Scandium and phosphorus co-doped perovskite oxides as high-performance electrocatalysts for the oxygen reduction reaction in an alkaline solution

The requirement for a sustainable and renewable energy has inspired substantial interests in designing and developing earth-abundant and high-effectiveness electrocatalysts/electrodes for fuel cells and metal-air batteries, in which oxygen reduction reaction(ORR) plays a crucial role. Perovskite oxides have acquired rapid attention as ORR electrocatalysts to replace noble-metal-based catalysts owing to their intrinsic electrocatalytic activity, compositional and structural flexibility. Herein, we report a new Sc and P co-doped perovskite oxide(La_(0.8)Sr_(0.2)Mn_(0.95)Sc_(0.025)P_(0.025)O_(3-δ), LSMSP) as an active and robust electrocatalyst for the ORR in an alkaline solution. LSMSP electrocatalyst shows superior ORR activity and stability than those of pristine La_(0.8)Sr_(0.2)MnO_(3-δ)(LSM), Sc-doped LSM and P-doped LSM due to the optimized average valence of Mn ions, the large surface area, the smaller particle size and the synergetic effect introduced by the co-doping. Moreover, compared to the benchmark Pt/C electrocatalyst, LSMSP electrocatalyst displays comparable ORR activity and superior durability. These above results suggest that the co-doping strategy of Sc and P into perovskites is a useful method to design high-performance electrocatalysts for the ORR, which can be used in other electrocatalysis-based applications.     

One-step scalable preparation of N-doped nanoporous carbon as a high-performance electrocatalyst for the oxygen reduction reaction

N-doped porous carbon materials have been prepared by a simple one-step pyrolysis of ethylenediaminetetraacetic acid (EDTA) and melamine in the presence of KOH and Co(NO₃)₂·6H₂O. The combination of the high specific area (1485 m²·g^?1), high nitrogen content (10.8%) and suitable graphitic degree results in catalysts exhibiting high activity (with onset and half-wave potentials of 0.88 and 0.79 V vs the reversible hydrogen electrode (RHE), respectively) and four-electron selectivity for the oxygen reduction reaction (ORR) in alkaline medium—comparable to a commercial Pt/C catalyst, but far exceeding Pt/C in stability and durability. Owing to their superb ORR performance, low cost and facile preparation, the catalysts have great potential applications in fuel cells, metal-air batteries, and ORR-related electrochemical industries.      

Transition metal phosphorus trisulfides as battery cathodes

The transition metal dichalcogenides, such as TiS₂, have been reported to perform well as cathodes in ambient temperature lithium batteries. It has been found that the layered, transition metal phosphorus trisulfides also exhibit electrochemical activity. Nickel phosphorus trisulfide will react with more than four lithium resulting in a cell with a theoretical energy density double that of titanium disulfide.     

Nitrogen,phosphorus co-doped carbon cloth as self-standing electrode for lithium-iodine batteries

Nano Research - Rechargeable lithium-iodine (Li-I2) battery is a promising energy storage system because of the high energy and power density. However, the shuttle effects of iodine species and the...     

Ketjenblack carbon supported amorphous manganese oxides nanowires as highly efficient electrocatalyst for oxygen reduction reaction in alkaline solutions

A composite air electrode consisting of Ketjenblack carbon (KB) supported amorphous manganese oxide (MnOx) nanowires, synthesized via a polyol method, is highly efficient for the oxygen reduction reaction (ORR) in a Zn-air battery. The low-cost and highly conductive KB in this composite electrode overcomes the limitations due to low electrical conductivity of MnOx while acting as a supporting matrix for the catalyst. The large surface area of the amorphous MnOx nanowires, together with other microscopic features (e.g., high density of surface defects), potentially offers more active sites for oxygen adsorption, thus significantly enhancing ORR activity. In particular, a Zn-air battery based on this composite air electrode exhibits a peak power density of ～190 mW/cm2, which is far superior to those based on a commercial air cathode with Mn3O4 catalysts.