介孔炭材料应用于电化学催化的研究进展

由于介孔炭材料具有高比表面、均一可调的孔径尺寸和形貌、良好的导电性和化学稳定性等优点,已被广泛应用到催化、吸附、分离和电化学储能等领域.近年来,多组分的掺杂与复合使介孔炭材料拥有可调变的功能性,已成为材料领域研究的一个热点.本文首先介绍介孔炭材料的合成,包括软模板法、硬模板法和无模板法等.接着论述介孔炭及其复合材料在电...     

Enhanced CO Affinity on Cu Facilitates CO2 Electroreduction toward Multi-Carbon Products

Electrochemical CO₂ reduction reaction (CO₂RR) is a promising strategy for waste CO₂ utilization and intermittent electricity storage. Herein, it is reported that bimetallic Cu/Pd catalysts with enhanced *CO affinity show a promoted CO₂RR performance for multi-carbon (C2+) production under industry-relevant high current density. Especially, bimetallic Cu/Pd-1% catalyst shows an outstanding CO₂-to-C2+ conversion with 66.2% in Faradaic efficiency (FE) and 463.2 mA cm⁻² in partial current density. An increment in the FE ratios of C2+ products to CO  for Cu/Pd-1% catalyst further illuminates a preferable C2+ production. In situ Raman spectra reveal that the atop-bounded CO is dominated by low-frequency band CO on Cu/Pd-1% that leads to C2+ products on bimetallic catalysts, in contrast to the majority of high-frequency band CO on Cu that favors the formation of CO. Density function theory calculation confirms that bimetallic Cu/Pd catalyst enhances the *CO adsorption and reduces the Gibbs free energy of the C C coupling process, thereby favoring the formation of C2+ products.     

Study of the electrochemical oxidation and reduction of C.I. Reactive Orange 4 in sodium sulphate alkaline solutions

Synthetic solutions of hydrolysed C.I. Reactive Orange 4, a monoazo textile dye commercially named Procion Orange MX-2R (PMX2R) and colour index number C.I. 18260, was exposed to electrochemical treatment under galvanostatic conditions and Na₂SO₄ as electrolyte. The influence of the electrochemical process as well as the applied current density was evaluated. Ti/SnO₂–Sb–Pt and stainless steel electrodes were used as anode and cathode, respectively, and the intermediates generated on the cathode during electrochemical reduction were investigated. Aliquots of the solutions treated were analysed by UV–visible and FTIR-ATR spectroscopy confirming the presence of aromatic structures in solution when an electro-reduction was carried out. Electro-oxidation degraded both the azo group and aromatic structures. HPLC measures revealed that all processes followed pseudo-first order kinetics and decolourisation rates showed a considerable dependency on the applied current density. CV experiments and XPS analyses were carried out to study the behaviour of both PMX2R and intermediates and to analyse the state of the cathode after the electrochemical reduction, respectively. It was observed the presence of a main intermediate in solution after an electrochemical reduction whose chemical structure is similar to 2-amino-1,5-naphthalenedisulphonic acid. Moreover, the analysis of the cathode surface after electrochemical reduction reveals the presence of a coating layer with organic nature.     

Development of catalytic activity protocol for electrochemical reduction of carbon dioxide to value added products

Utilization of carbon dioxide for the production of value added products is a challenging task. Electrochemical reduction of carbon dioxide is one of the most promising techniques to convert the carbon dioxide into value added products. However, the development and selection of a suitable electrocatalyst is not so straightforward. The main problems are non-selectivity of the electrocatalyst toward CO₂ reduction, simultaneous hydrogen evolution reaction, and low efficiency of the process. To overcome these problems, many electrocatalysts have been studied and reported in the literature. However, there is no effective guideline to screen the electrocatalysts in a quick and simple way. Moreover, it is found that the method used for the screening of electrocatalyst is not accurate and has anomalies. Therefore, in this paper, a simple and quick protocol based on half-cell tests is proposed. The method provides a first-hand prediction about the electrochemical activity of an electrocatalyst toward electrochemical reduction of carbon dioxide. The protocol was validated and compared along with confirming the results by product analysis of the electrochemical reduction of CO₂ using full electrochemical reactor. The method was found satisfactory for the preliminary screening of electrocatalyst to reduce carbon dioxide electrochemically.     

温度对碳热还原/氮化法合成氮化硅的影响

碳热还原/氮化合成Si3N4在1 300~1 600℃下N2或N2-H2混合气中进行。反应物由非晶Si O2与C粉以1∶4.5摩尔比混合、压片。产生的CO由红外传感器监测,样品中氧、氮、碳含量由LECO元素分析仪测得,混合物各相由X射线衍射(XRD)检测。Si O2还原反应在1 300℃以下开始,速率随温度升高增大;温度高于1 570℃时,速率因反应物表面被生成物覆盖降低。由于还原产物CO平衡分压差别小,选择生成Si3N4或Si C的临界温度不明显。碳热还原/氮化法合成氮化硅的原理需进一步探讨。     

共平面低功耗CO气体传感器的设计及制作

设计了一种新型的共平面微结构气体传感器,利用MEMS技术制作了传感器样品.实验测得该传感器对于体积分数为50×10~(-6)CO气体的灵敏度为8.6(R0/R),功耗为82mW,响应时间约5s,恢复时间约22s,该传感器的灵敏度是同种敏感材料烧结型传感器(测体积分数50×10~(-6) CO气体)的2.5倍,而功耗却是同种敏感材料烧结型传感器的1/2,是一种具备了体积小、重量轻、功耗低、灵敏度高、便于与其它器件集成等特点,而且制作工艺简单,成本较低的微结构CO气体传感器.     

玻碳电极上核黄素的电化学行为研究

用循环伏安法和线性扫描伏安法探讨核黄素在玻碳电极上的电化学行为。在多种缓冲液中测试,发现HAe—NaAe作为缓冲液时电化学氧化还原峰形最好,峰电流较大,电化学过程表现出良好的可逆性,电子转移数n为2,扩散系数D0为2．3×10^-5cm^2·s^-1;改变缓冲液的pH值,峰电流随pH值增大而负移,说明其在电极表面有吸附作用;光照后核黄素在-0．35V和-0．45V附近出现两个还原峰;分析实验数据可得,在1．0×10^-4mol/L数量级时还原峰峰电流与其浓度呈现良好的线性关系。     

酚醛树脂基活性炭微球的电化学性能Ⅱ.作为EDLC电极材料的活性炭微球的制备及电化学性能

用直流恒流循环法考察在不同的活化条件下得到的酚醛树脂活性炭微球作为双电层电容器电极的电化学性能。结果表明，要得到高比电容的电容器电极材料，水蒸气活化的最佳条件为：在800℃下活化1h，水蒸气的量控制为氮气量的40％。在此条件下得到的酚醛树脂活性炭微球作为电极具有良好的循环充放电性能，比电容可达到143F／g，充放电效率高达98％。在2．0nm～7．5nm之间的孔对活性炭微球的比电容影响显著。     

Synthesis of Ru/multiwalled carbon nanotubes by microemulsion for electrochemical supercapacitor

An efficient way to decorate multiwalled carbon nanotubes with Ru had been developed. In this method, Ru nanoparticles were prepared by water-in-oil reverse microemulsion, and the produced Ru anchored on MWCNTs. Transmission electron microscopy (TEM) result showed that RuO₂ nanoparticles had the uniform size distribution after electrochemical oxidation. Energy dispersive X-rays (EDX) spectra elucidated the presence of ruthenium oxide in the as-prepared composites after electrochemical oxidation. Cyclic voltammetry result demonstrated that a specific capacitance of deposited ruthenium oxide electrode was significantly greater than that of the pristine MWCNTs electrode in the same medium.     

Preparation and electrochemical properties of multiwalled carbon nanotubes-nickel oxide porous composite for supercapacitors

Porous nickel oxide/multiwalled carbon nanotubes (NiO/MWNTs) composite material was synthesized using sodium dodecyl phenyl sulfate as a soft template and urea as hydrolysis-controlling agent. Scanning electron microscopy (SEM) results show that the as-prepared nickel oxide nanoflakes aggregate to form a submicron ball shape with a porous structure, and the MWNTs with entangled and cross-linked morphology are well dispersed in the porous nickel oxide. The composite shows an excellent cycle performance at a high current of 2 A g⁻¹ and keeps a capacitance retention of about 89% over 200 charge/discharge cycles. A specific capacitance approximate to 206 F g⁻¹ has been achieved with NiO/MWNTs (10 wt.%) in 2 M KOH electrolyte. The electrical conductivity and the active sites for redox reaction of nickel oxide are significantly improved due to the connection of nickel nanoflakes by the long entangled MWNTs.     

碳热还原法制备Sn-C复合材料及其性能

用碳热还原法制备了Sn-C复合材料,通过XRD及SEM对其进行表征,并通过恒流充放电循环和慢速扫描循环伏安等方法对其电化学嵌脱锂性能做了研究.结果表明:SnO2碳热还原成金属Sn,晶粒尺寸约为42.8nm.该材料的首次嵌脱锂比容量分别可以达到1024.9和632.8mAh/g,循环15周以后的脱锂比容量为395.9mAh/g.     

静电纺丝法制备多孔纳米炭纤维及其电化学性能研究

分别以聚乙烯醇(PVA)/热固性酚醛树脂(PF)/碳酸钾(K2CO3)和PVA/PF的水溶液为纺丝原液,通过静电纺丝、固化和炭化处理制得多孔纳米炭纤维。利用扫描电子显微镜(SEM)、低温氮气吸脱附等对所制多孔炭纳米纤维进行表征,并将所制多孔炭纤维作为模拟电容器电极材料,利用循环伏安和恒电流充放电进行了电化学性能测试。结果表明:纺丝原液中加入K2CO3后所制多孔纳米炭纤维的比表面积增大(从564 m.2g-1提高到668 m.2g-1),电化学性能提高(在电流密度为0.2 A.g-1的情况下,比电容由165 F.g-1提高到178 F.g-1)。     

Recent development of perovskite oxide-based electrocatalysts and their applications in low to intermediate temperature electrochemical devices

As a consequence of the depletion of fossil fuels and an increasing population, the global energy crisis has driven researchers to explore innovative energy storage and conversion (ESC) devices, such as fuel cells, electrolyzers and chemical looping systems. In order to enhance the energy conversion efficiency of these electrochemical devices, high performance and stable electrocatalysts are essential to accelerate the sluggish electrochemical kinetics, e.g. oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and redox reaction. In recent years, as cost-effective and high-efficient catalysts, perovskite oxides have attracted much attention. In addition, the potential of perovskite electrocatalysts may be further boosted due to their flexible composition and tunable electronic structures. This review provides the readers with a comprehensive understanding and updated information of improvements towards the electrocatalytic performances of perovskite oxides. It will focus on research papers regarding low to intermediate temperature electrochemical devices, e.g., water splitting, fuel cells, chemical looping technology and three-way catalysis (TWC) published over the last five years. Various design strategies for optimizing the conductivity and catalytic activity of perovskite are discussed in detail. In the end, this review discusses challenges for the future researches in regard to perovskite based electrocatalysts.     

Synthesis of polyoxometalates-functionalized carbon nanotubes composites and relevant electrochemical properties study

Carbon nanotubes (CNTs)-based polyoxometalates (POMs)-functionalized nanocomposites were synthesized by simply functionalizing CNTs with Keggin and Dawson-type POMs. The positively charged polyelectrolyte poly (diallyldimethylammonium chloride) (PDDA) was introduced to assemble negatively charged POMs and CNTs. The composition, structure and morphology were investigated by UV-visible (UV-vis), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Cyclic voltammetry (CV) was employed to investigate the electrochemical properties of the resulting nanocomposites. The cyclic voltammograms indicate that the electrochemical properties of POMs are fully maintained. Functionalizing CNTs with POMs not only retains the unique properties of nanotubes, but also endows CNTs with the reversible redox activity of POMs.     

添加多壁纳米碳管活性炭电极材料的电化学电容特性

在活性炭电极材料中，用多壁纳米碳管作导电添加剂替代传统的炭黑、石墨粉等可较大地改善电极材料的性能。当添加质量分数为5％的多壁纳米碳管时，活性炭电化学电容器的比电容量由添加同量炭黑的130F／g增加到185F／g，同时提高了活性炭电容器的频率响应性能。基于该研究结果试制出不同规格的添加多壁纳米碳管的活性炭电化学电容器样品，结果表明添加多壁纳米碳管的活性炭电极材料具有良好的电化学电容特性。     

Preparation of graphene nanosheets/SnO2 composites by pre-reduction followed by in-situ reduction and their electrochemical performances

The Graphene nanosheets/SnO₂ composites were synthesized using stannous chloride to restore the semi-reduction graphene oxide (SRGO) under a simple hydrothermal reduction procedure. First graphene oxide was pre-reduced by glucose for a certain time to get SRGO, which keeps the good water-solubility of graphite oxide (GO) and has a good conductivity like graphene nanosheets. The higher electrostatic attraction between SRGO and Sn²⁺ makes SnO₂ nanoparticles tightly anchor on the graphene sheets in the hydrothermal reduction process. The formation mechanism of the composite was investigated by SEM, TEM, XRD, AFM and Raman. Moreover, the electrochemical behaviors of the Graphene nanosheets/SnO₂ nanocomposites were studied by cyclic voltammogram, electrical impedance spectroscopy (EIS) and chronopotentiometry. Results showed that the Graphene nanosheets/SnO₂ composites have excellent supercapacitor performances: the specific capacitance reached 368 F g⁻¹ at a current density of 5 mA cm⁻², and the energy density was much improved to 184 Wh kg⁻¹ with a power density of 16 kW kg⁻¹, and capacity retention was more than 95% after cycling 500 cycles with a constant current density of 50 mA cm⁻². The experimental results and the thorough analysis described in this work not only provide a potential electrode material for supercapacitors but also give us a new way to solve the reunification of the graphene sheets.     

电化学阻抗解析多壁碳纳米管/活性炭的电化学性能

以石油焦为原料化学活化制得活性炭(Activated carbon,AC),在此AC中加入不同量的多壁碳纳米管(Multi-walled carbon nanotubes,MWCNTs)作为超级电容器电极材料.依据交流阻抗谱中阻抗与电容关系,区分有效容量和内阻造成的能量损失,评价了超级电容器的性能.结果表明:加入质量分数3％～15％ MWCNTs的AC电极,实部电容高于纯AC电极,虚部电容则随着MWCNTs添加量的增加而显著降低.且其实部电容分数随MWCNTs加入量的增加呈上升趋势,虚部电容分数则随MWCNTs加入量增加而降低.在AC电极中加入MWCNTs,在降低电极内阻的同时可有效提高超级电容器的储能效率,并降低弛豫时间,提高其频率特性,改善电容行为.     

Studying the growth of carbon nanotubes on carbon fibers surface under different catalysts and electrochemical treatment conditions

A special electrochemical anodic oxidation (EAO) method was applied to modify the surface of carbon fibers (CFs) with fatty alcohol polyoxyethylene ether phosphate (O₃P), triethanolamine (TEA), fatty alcohol polyoxyethylene ether ammonium phosphate (O₃PNH₄), and ammonium bicarbonate (NH₄HCO₃) used as the electrolyte respectively. Then different catalysts, including Ni, Co, and Cu, were used to catalyze the growth of carbon nanotubes (CNTs) on the surface of CFs. The variation regulation of structure and property of CNTs on CFs surface was investigated by different methods. The results showed that the optimal effect of surface modification of CFs was achieved when O₃PNH₄ served as an electrolyte and the optimal electrochemical treatment intensity (ETI) was 100C/g. Also, with temperature variety, there are different microstructure changes for CNTs that adopt different catalysts. Through the experiment, a uniform catalyst coating was obtained on the surface of CFs after reduction process, which laid the foundation for the growth of uniform and regular CNTs.