Electrodeposited Nickel/Platinum Alloy as a Biosensor for Acetyl Choline

Nickel and platinum find extensive use in preparation of biosensors. In the present work, Ni/Pt alloy was plated on graphite to make acetylcholine sensor. The microstructure, surface composition and electrochemical performance of the electrode was analyzed by different techniques. The sensing performance was evaluated by cyclic voltammetry. The prepared alloy plate exhibited very good linear relationship between acetyl choline concentration and response current. The sensitivity and reproducibility of the prepared electrode were found better than other nickel electrodes reported.     

直接甲醇燃料电池阴极电催化剂的研究进展

直接甲醇燃料电池(DMFC)功率密度高，燃料甲醇价格低廉、储存和携带方便，特别适合作为电动车和小型电子设备的电源，是目前燃料电池研究领域的一个热点。本文介绍了40年来DMFC阴极电催化剂的发展历史及现状，并针对目前严重影响DMFC性能的“甲醇透过”问题，阐述了研制耐甲醇阴极电催化剂的重要性，讨论了今后DMFC阴极电催化剂的发展趋势。     

Comprehensive and High-throughput Electrolysis of Water and Urea by 3–5 nm Nickel and Copper Coordination Polymers

Metal-organic coordination polymers (CP) have attracted the scientific attention for electrochemical water oxidation as it has the similar coordination structure like natural photosynthetic coordinated complex. However, the harsh synthesis conditions and bulky nature pose a major challenge in the field of catalysis. Herein, 3–5 nm CP particles synthesized at room temperature using aqueous solutions of Ni²⁺/Cu²⁺ and 2,5-dihydroxyterepthalic acid as precursor were applied for alkaline water and urea electrolysis. The overpotential required is only 300 mV at 10 mA cm⁻² by Nano-Ni CP for water oxidation, with turnover frequency (TOF) of 21.4 s⁻¹ which is around 8 times higher than its bulk-counterpart. Overall water and urea splitting were achieved with Nano-Cu (−) ∥ Nano-Ni (+) couple on Ni foam at 1.69 and 1.52 V to achieve 10 mA cm⁻², respectively. High electrochemical surface area (ECSA), high TOF, and enhanced mass diffusion are found to be the key parameters responsible for the state-of-the-art water and urea splitting performances of nano-CPs as compared to their bulk counterparts.     

The preparation of ionic liquid based iron phosphate/CNTs composite via microwave radiation for hydrogen evolution reaction and oxygen evolution reaction

Water electrolysis is a promising method for hydrogen production, so the preparation of low-cost and efficient electrocatalysts with a quick and simple procedure is crucial. Herein, iron phosphate (Fe₇(PO₄)₆) was prepared via microwave radiation using ionic liquid (IL) as iron and phosphorus dual-source. This method is simple and rapid, and the product can be directly used as electrocatalysts without further treatment. The experimental results show that the IL can influence the morphology and electrocatalytic performance. Moreover, the addition of carbon nanotubes (CNTs) is favorable for formation of iron phosphate nanoparticles to improve the catalytic activities. As hydrogen evolution reaction (HER) catalyst, this iron phosphate/CNTs exhibits an onset overpotential of 120 mV, Tafel slope of 32.9 mV dec^-1, and current densities of 10 mA cm⁻² at overpotential of 185 mV. Then, it obtains a good activity for oxygen evolution reaction (OER) with a low onset potential of 1.48 V, Tafel slope of 73.3 mV dec^-1, and it only needs an overpotential of 300 mV to drive the 10 mA cm⁻². This bifunctional catalyst also shows good durability for HER and OER. This microwave-assisted method provides an outstanding strategy to prepare iron phosphate in a simple and fast process with good catalytic performance for water splitting.     

可控表面磷原子修饰提升超细W2C纳米颗粒电解水析氢反应性能

研究高活性和稳定性的非贵金属基析氢催化剂对解决当前能源危机和环境污染问题具有重要意义.碳化钨具有与贵金属Pt类似的d带电子结构,因而成为一类新兴的非贵金属析氢催化剂,受到广泛关注.磷掺杂是提高催化剂析氢活性的有效方法之一,然而目前最常见的构筑磷掺杂方法是使用多金属氧酸盐(POMs,如H3PW12O40),其固定的W/P原子比导致W2C中的掺杂浓度难以调控,并且磷掺杂主要是进入碳载体而不是碳化物本身,从而导致无法明确杂原子对其电催化析氢活性的贡献.本文采用植酸(PA)为磷源设计合成了可控磷掺杂W2C纳米颗粒,并探讨了催化剂组分、杂原子掺杂位置与析氢性能之间的关系.深入研究了磷掺杂碳化钨(WCP)的化学结构和析氢活性.与原始的W2C催化剂相比,WCP具有更高的本征活性、更快的电子转移速率和更多的活性位数量,并且在酸性和碱性条件下均表现出较好的析氢性能.特别是过电位为-200 mV时,WCP催化剂的本征活性在酸性和碱性条件下分别为0.07和0.56 H2 s-1,高出纯W2C(0.01和0.05 H2 S-1)数倍.同时,在电流密度为-10 mA cm-2时,优化后的WCP催化剂在酸性和碱性条件下的析氢过电位分别降低了96和88 mV.XPS及EDS元素分析结果表明,随磷源添加量增加,磷掺杂从碳化钨表面逐渐向内部扩散,进一步说明磷取代位置与析氢活性之间的构效关系,高浓度的表面磷取代可以加速质子捕获过程,从而显著提高其析氢活性,而过量的内部磷取代会破坏W2C结构,降低电子转移速率,从而导致析氢性能下降.利用密度泛函理论计算深入研究了WCP具有较好析氢性能的原因,与内部磷取代相比,表面磷取代会使碳化钨表现出更合适的氢吸附自由能,并且更加有效地降低了氢释放势垒,从而优化了析氢反应动力学.综上,本文为元素掺杂工艺提供了新的思路,同时研究了表面异质原子对析氢活性的关键作用,为该类催化材料的构效关系研究提供了新思路.     

碱性介质中氢氧化反应电催化剂的开发:从机理认识到材料设计

阴离子交换膜(AEM)燃料电池因具有使用非贵金属作为催化剂的优点而受到广泛关注.然而,在碱性体系中,AEM燃料电池中氢氧化反应(HOR)的反应动力学比在酸性介质中的慢两个数量级.针对HOR在碱中动力学缓慢的问题,有两种主要的理论来解释,(1)pH相关的氢结合能作为主要影响因素来控制HOR动力学的理论;(2)质子和氢氧根离子的吸附共同作为影响因子来控制HOR在碱性条件下的动力学的双功能理论.本文首先讨论了在碱性电解质中可能的HOR反应机理及其Tafel性能变化.除了传统的Tafel-Volmer和Heyrovsky-Volmer-HOR机理外,还讨论了最新提出的氢氧根离子吸附参与的HOR机理来说明在酸性和碱性介质中HOR机理的差异.然后,总结了具有代表性的碱性HOR催化剂(如贵金属、合金、金属间化合物、镍基合金、碳化物、氮化物等),简要介绍了它们相应的HOR反应机理,从而进一步理解在碱性介质中不同基元反应步骤给HOR性能带来的差异.最后,提出了一种未来设计HOR碱性催化剂的可行性方案,为今后碱性环境下的HOR催化剂设计提供参考.     

Silver nanoparticle decorated poly(2-aminodiphenylamine) modified carbon paste electrode as a simple and efficient electrocatalyst for oxidation of formaldehyde

This work describes the promising activity of silver nanoparticles on the surface of a poly(2-amino diphenylamine) modified carbon paste electrode (CPE) towards formaldehyde oxidation. Electrodeposition of the conducting polymer film on the CPE was carried out using consecutive cyclic voltammetry in an aqueous solution of 2-aminodiphenylamine and HCl. Nitrogen groups in the polymer backbone had a Ag ion accumulating effect, allowing Ag nanoparticles to be electrochemically deposited on the surface of the electrode. The electrochemical and morphological characteristics of the modified electrode were investigated. The electro-oxidation of formaldehyde on the surface of electrode was studied using cyclic voltammetry and chronoamperometry in aqueous solution of 0.1 mol/L NaOH. The electro-oxidation onset potential was found to be around -0.4 V, which is unique in the literature. The effect of different concentrations of formaldehyde on the electrocatalytic activity of the modified electrode was investigated. Finally, the diffusion coefficient of formaldehyde in alkaline media was calculated to be 0.47 × 10^-6 cm²/s using chronoamperometry.     

基于氮掺杂碳载铁复合物的锌空电池氧阴极催化剂

迫在眉睫的环境和能源问题推动人类探索可行、可靠和可再生的能源技术.锌-空气电池和氢氧燃料电池等器件显示出高能量转换效率,但是仍有许多难题有待克服,例如阴极侧上缓慢的氧还原反应(ORR),以及高昂的成本极大地限制了铂基催化剂在商业上的广泛应用.因此,开发高性能的廉价ORR催化剂具有重要意义.过渡金属碳氮化合物(M-N-C, M=Co, Fe等)成为最有希望替代铂基催化剂的一类材料, M-N-C催化剂可以通过直接热解含有过渡金属、氮和碳物种的前驱体合成.然而热解时金属原子易团聚,多孔结构不能被有效地控制,导致相对较差的催化活性.目前, MOF衍生的催化剂在能源转化和储存技术中得到了广泛的关注,其具有丰富的氮含量、高比表面积和可调的孔道结构等特点.本文报道了一种简便可靠可控的合成铁氮共掺杂碳十二面体纳米结构催化剂的方法,并作为阴极电催化剂用于锌空气电池中,测试结果证实,合成的铁氮共掺杂的纳米碳具有与铂基材料相当的活性和更加优异的稳定性.表面吸附了的邻菲罗啉铁的ZIF-8在碳化过程中,氮基团能够结合铁形成Fe Nx结构单元,因此可得到铁氮共掺杂的电催化剂.粉末X射线衍射,扫描电镜证实ZIF-8的成功合成.经过热解得到的催化剂中Fe Nx或Fe Cx衍射峰较弱,表明样品中铁含量较低,存在部分无定型铁.通过拉曼光谱分析发现,引入的邻菲罗啉在热解过程中诱导了缺陷的形成,所以Fe-NCDNA-0的ID/IG比值明显高于NC.同时ID/IG随着铁含量的增加而减少,这是因为铁可以诱导石墨化,诱导效应随着铁含量的增加而增加.分析氮气吸附-脱附等温线得出,引入邻菲罗啉之后,比表面积增加;而铁的引入因其占据了微孔结构,导致比表面积下降.同时电镜证实Fe-NCDNA-2具有较大的形貌扭曲,使得该材料具有较大的比表面积.系统的电化学研究表明,氮掺杂有利于增强ORR活性,在引入铁之后形成高效的活性中心会进一步提高催化性能.因此, Fe-NCDNA-2在碱性条件下表现出优异的ORR性能.线性扫描伏安法曲线表明,铁氮共掺杂的材料表现出与Pt/C相似的性能,其中Fe-NCDNA-2的半波电位(E1/2)为0.863 V,比商业Pt/C的电位更正(E1/2=0.841 V).同时, Fe-NCDNA-2具有更加优异的稳定性,测试30000 s后的电流保持率为80%(Pt/C:64%).在中性介质中,合成的材料也展示了较高的ORR活性.Fe-NCDNA-2的E1/2=0.715 V,催化30000 s后电流保持率77%,均优于商业Pt/C催化剂.组装的锌空气电池进一步验证其作为氧还原催化剂实际应用的可行性.相比于以Pt/C为催化剂做空气阴极的电池,以Fe-NCDNA-2组装的电池表现出更高的开路电压,更高的功率密度(184 m Wcm^-2),以及更加优异的充放电循环稳定性.该工作也有利于启发研究人员探索类似的氮掺杂过渡金属碳材料在各种催化上的应用.     

Unstable Ni leaching in MOF-derived PtNi-C catalyst with improved performance for alcohols fuel electro-oxidation

Significance of unstable species leaching was for the first time demonstrated on MOF-derived catalysts by taking PtNi-C as an example, that was instructive for the relevant catalyst fabrication and performance study. PtNi-C catalyst was synthesized by combining Pt nanoparticles with Ni-BTC after annealing in the tube furnace and the unstable Ni species can be easily leached out in nitric acid, and the stable PtNi nanoparticles trapped in the graphite carbon layer were obtained. The greatly improved catalytic ability for alcohol fuels oxidation was verified by comparing the fresh and acid leached catalysts in terms of the high peak current density, specific and mass activity and rapid charge transfer kinetics and high catalytic stability. The current work guides the importance of unstable assistant promoter removal for the MOF derived catalysts.