三种碳材料上原位电沉积AuPt合金的催化性能

在碳纸（CP）及涂覆了碳粉科琴黑（KB）或石墨烯纳米片（GNs）的碳纸上,原位电沉积了AuPt合金,制备成CP/AuPt、CP/KB/AuPt、CP/GNs/AuPt三种空气电极。对比研究发现,以石墨烯纳米片为载体的CP/GNs/AuPt空气电极上,AuPt合金载量高,颗粒分散均匀,粒径约为100 nm左右,Au和Pt的含量分别为78.84%（n/n）和21.16%（n/n）。在0.1 mol·L^-1 KOH溶液中氧还原反应的起峰电势为0.93 V,催化活性和稳定性优于其他两种空气电极。分析认为,石墨烯纳米片具有高导电性、高比表面积以及较多的缺陷活性位点,有利于AuPt合金在其上均匀电沉积且沉积载量较高,同时GNs本身具有一定的催化活性,两者能够产生协同催化作用,提高了CP/GNs/AuPt电极的催化性能。     

Pt微粒修饰纳米纤维聚苯胺电极对甲醇氧化电催化

以脉冲电流法制备的纳米纤维状聚苯胺(PANI)为Pt催化剂载体，用它制备了甲醇阳极氧化的催化电极Pt/（nano-fibular PANI）.研究结果表明, Pt/（nano-fibular PANI）电极对甲醇氧化具有很好的电催化活性,并有协同催化作用.在相同的Pt载量条件下， Pt/（nano-fibular PANI）电极比Pt微粒修饰的颗粒状聚苯胺电极Pt/(granular PANI)具有更好的电催化活性.此外， Pt的电沉积修饰方法同样影响Pt/（nano-fibular PANI）电极对甲醇氧化的催化活性.脉冲电流法沉积Pt形成的复合电极较循环伏安法电沉积得到的Pt复合电极具有更优异的催化活性.     

离子交换-电沉积法制备高Pt利用率多孔电极

采用离子交换-电沉积的方法(Ion-exchange/electrodeposition,IEE)制备了一种高Pt利用率催化电极,对所制备电极的表面形貌、催化活性及单电池性能用线性扫描伏安(LSV)、扫描电镜(SEM)、透射电镜(TEM)和单电池测试进行了表征. 结果表明,通过电极制备工艺和离子交换-电沉积参数的调控,能够消除碳载体表面官能团的影响,使铂阳离子只与全氟磺酸树脂(Nafion)上的H⁺进行交换. 在无铂离子的电解质中,将被交换的铂阳离子还原到与Nafion接触的碳载体上,使每一个铂纳米粒子都处于气体多孔电极的三相界面上,有效地调控铂纳米粒子的尺寸和分散度. 单电池测试表明,以铂载量为0.014 mgPt•cm^-2的IEE电极组装的电池的输出功率与铂载量为0.3 mgPt•cm-²的Nafion粘接Pt/C电极相当.     

氮掺杂还原氧化石墨烯负载铂催化剂的制备及甲醇电氧化性能

采用高温热解聚苯胺修饰的氧化石墨烯(PANI-GO),得到了氮掺杂的还原氧化石墨烯碳材料(N-RGO),以其负载Pt制备了Pt/N-RGO纳米结构电催化剂.采用透射电镜(TEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)谱及拉曼光谱等技术对N-RGO和Pt/N-RGO的形貌及结构进行了表征,用循环伏安、计时电流等电化学技术研究了Pt/N-RGO电极催化剂对CO溶出反应和甲醇电氧化反应的催化性能.结果表明:高温热解PANIGO可同时实现GO的还原及其氮掺杂的过程,氮掺杂引起还原氧化石墨烯碳材料表面缺陷结构和导电性的增加;与相应的未掺杂氮样品Pt/RGO相比较,Pt/N-RGO样品上Pt颗粒的分散更均匀,显示出更强的抗CO毒化能力和更高的甲醇电氧化催化活性及稳定性.     

Ti基纳米TiO_2-CNT-Pt复合电极制备、表征及电化学性能

以电合成前驱体Ti(OEt)4直接水解法和电化学扫描电沉积法制备Ti基纳米TiO2-CNT-Pt(Ti/nanoTiO2-CNT-Pt)复合电极.透射电镜(TEM)和X射线衍射(XRD)测试表明,锐钛矿型纳米TiO2粒子(粒径5～10nm)和碳纳米管(CNT)结合形成网状结构,Pt纳米粒子(平均粒径9nm)均匀地分散在纳米TiO2-CNT复合膜表面.循环伏安及计时电流测试表明,Ti/nanoTiO2-CNT-Pt复合电极具有高活性表面,对甲醇的电化学氧化具有高催化活性和稳定性,Pt载量为0.32mg/cm2时,常温常压下甲醇氧化峰电流达到480mA/cm2.     

Pt/g-C_3N_4/KB纳米复合催化剂的制备及其甲醇氧化性能

采用溶液中等离子放电法制备出了Pt纳米颗粒,用热氧化刻蚀和水热法成功的对石墨相氮化碳(g-C_3N_4)进行处理进而均匀吸附在科琴黑(KB)表面,最终制备出了Pt/g-C_3N_4/KB纳米复合催化剂。通过XRD分析,扫描电镜,透射电镜和电化学工作站探究了催化剂的组成、结构、颗粒大小以及电化学性能。Pt/g-C_3N_4/KB纳米复合催化剂展现出了良好的甲醇电氧化性能,性能的提升可能是由于g-C_3N_4良好的化学稳定性,N元素的存在改变Pt外层电子结构从而提高催化活性,这些因素提高了Pt的催化效率。     

铂/聚邻甲基苯胺/碳材料掺杂碳糊电极对甲醇的催化氧化

以石墨和液体石蜡油为主要原料,分别制备了掺杂不同量多壁碳纳米管(MWCNT)、石墨烯(GRA)、电容活性炭(YEC)和电池活性炭(YBC)的多种碳糊底电极Y-CPE(Y代表各种掺杂碳材料,CPE代表纯碳糊电极).采用恒电位法在-0.10 V(vs.Ag/Ag Cl)电位下将铂电沉积到这些电极上.结果表明,当电池碳的含量为14%时,Pt/YBC-CPE(14%)复合电极对甲醇具有最好的电催化氧化活性.采用恒电位方法在0.85 V(vs.Ag/Ag Cl)电位下将聚邻甲基苯胺(POT)电聚合沉积到纯碳糊电极CPE和含有电池碳的YBC-CPE(14%)电极上,得到复合电极POT/CPE和POT/YBC-CPE(14%),再通过恒电位方法将铂电沉积到这2个复合电极上.扫描电镜(SEM)观察结果表明,在Pt/CPE,Pt/YBC-CPE(14%),Pt/POT(6.5 mC)/CPE和Pt/POT(6.5 mC)/YBC-CPE(14%)4个复合电极中,在Pt/POT/YBC-CPE(14%)复合电极上的铂粒子的尺寸最小,并且Pt/POT(6.5 mC)/YBC-CPE(14%)复合电极电催化氧化甲醇活性最高.在POT(6.5 mC)/CPE和POT(6.5 mC)/YBC-CPE(14%)上Pt纳米颗粒的电沉积过程是一个近似的3D成核过程.研究还发现,复合电极Pt/POT/CPE和Pt/POT/YBC-CPE电催化氧化甲醇的活性随POT膜厚度的增加先增大后减少,存在一个最佳的膜厚度.     

Pt纳米粒子修饰的多孔硅电极的制备及其电催化性能

通过循环伏安法电沉积使直径约为7 nm的Pt纳米粒子均匀地分散于多孔硅表面, 拟用作微型质子交换膜燃料电池的催化电极. 与刷涂法相比较, 电沉积Pt纳米粒子的多孔硅电极(Pt/Si)呈现出高的Pt利用率和增强的电催化活性. 当Pt载量为0.38 mg•cm−2时, 其电化学活性比表面积高达148 cm2•mg−1, 是刷涂相近质量的纳米Pt/C催化剂的多孔硅电极Pt-C/Si的2倍多；该修饰电极对甲醇氧化也呈现了增强的催化性能和好的稳定性, 在0.5 V(vs SCE)极化1 h后电流密度为4.52 mA•cm−2, 而刷涂了相近Pt量的Pt-C/Si电极的电流密度只有0.36 mA•cm−2.     

电化学方法制备高分散Pt/CMK-3及其对甲醇电化学催化性能

采用直接电化学还原法在介孔碳(CMK-3)载体上直接电沉积高分散的铂纳米颗粒,制备CMK-3复合铂纳米颗粒电极(Pt/CMK-3)。 通过透射电子显微镜分析发现,铂纳米颗粒非常均匀的分布在CMK-3上,平均粒径约5 nm。 通过循环伏安测试,分析了催化剂不同负载铂含量时氯铂酸的利用率,在理论铂质量分数为20%时,这种方法制备的Pt/CMK-3所使用的氯铂酸的利用率最高,在1 mol/L CH3OH+0.5 mol/L H2SO4溶液中循环伏安测试电流密度达到382 A/g。 在相同实验条件下,Pt/CMK-3电极对甲醇电催化活性远高于Pt/XC-72(炭黑)电极和用常规电沉积方法制备的Pt/CMK-3电极。     

氮掺杂还原氧化石墨烯负载铂催化剂的制备及甲醇电氧化性能

采用高温热解聚苯胺修饰的氧化石墨烯（PANI-GO）,得到了氮掺杂的还原氧化石墨烯碳材料（N-RGO）,以其负载Pt 制备了Pt/N-RGO纳米结构电催化剂. 采用透射电镜（TEM）、X射线光电子能谱（XPS）、X 射线衍射（XRD）谱及拉曼光谱等技术对N-RGO和Pt/N-RGO的形貌及结构进行了表征,用循环伏安、计时电流等电化学技术研究了Pt/N-RGO电极催化剂对CO溶出反应和甲醇电氧化反应的催化性能. 结果表明：高温热解PANIGO可同时实现GO的还原及其氮掺杂的过程,氮掺杂引起还原氧化石墨烯碳材料表面缺陷结构和导电性的增加;与相应的未掺杂氮样品Pt/RGO相比较,Pt/N-RGO样品上Pt 颗粒的分散更均匀,显示出更强的抗CO毒化能力和更高的甲醇电氧化催化活性及稳定性.     

Effect of magnetic field on properties of AuPt particles magneto-electrodeposited on carbon paper

AuPt nano particles are bi-functional catalysts for Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) that were taken place on air electrodes in lithium air batteries. Magnetic field has been applied during electrodeposition for the preparation of AuPt particles. With the increase of the magnetic flux density under constant current density, the grain size decreases from about 1μm to 200nm and the activity of the AuPt catalyst increases. The magnetic field oriented vertical to the electric field has a promotion effect on increasing the catalytic ability of AuPt/carbon electrode. By pulse plating, the grain size decreases to about 100nm. By adjusting parameters of the electric field and the magnetic field, controllable in-situ preparation of AuPt catalyst with various morphology and catalytic activity could be achieved.     

氮化钨-钨/掺氮有序介孔碳复合材料的制备及其氧还原性能

采用软模板法制备了氮化钨-钨/掺氮有序介孔碳复合材料（WN-W/NOMC）,作为一种高比表面积且价格低廉的阴极氧还原反应催化剂。通过适量添加尿素来改变复合材料中的氮含量,在掺氮量为7%（w/w）时,实验发现材料能够保持完整有序介孔结构,测试其比表面积高达835 m²·g^-1,透射电子显微镜（TEM）测试结果显示其催化颗粒均匀地分散在氮掺杂有序介孔碳载体上。在O₂饱和的0.1 mol·L^-1 KOH溶液中测试了材料的氧还原催化性能（ORR）,显示其起始电位为0.87 V（vs RHE）,极限电流密度为4.49 mA·cm^-2,氧还原反应的转移电子数为3.4,接近于20%（w/w）商业Pt/C的3.8,说明该材料表现出近似4电子的氧还原反应途径。研究结果表明,WN-W/NOMC的催化性能虽然稍弱于商业铂碳（0.99 V,5.1 mA·cm^-2）,但其具有远超铂碳的循环稳定性和耐甲醇毒化能力。     

氮化钨-钨/掺氮有序介孔碳复合材料的制备及其氧还原性能

采用软模板法制备了氮化钨-钨/掺氮有序介孔碳复合材料(WN-W/NOMC),作为一种高比表面积且价格低廉的阴极氧还原反应催化剂。通过适量添加尿素来改变复合材料中的氮含量,在掺氮量为7%(w/w)时,实验发现材料能够保持完整有序介孔结构,测试其比表面积高达835 m~2·g~(-1),透射电子显微镜(TEM)测试结果显示其催化颗粒均匀地分散在氮掺杂有序介孔碳载体上。在O_2饱和的0.1 mol·L~(-1 )KOH溶液中测试了材料的氧还原催化性能(ORR),显示其起始电位为0.87 V(vs RHE),极限电流密度为4.49 mA·cm~(-2),氧还原反应的转移电子数为3.4,接近于20%(w/w)商业Pt/C的3.8,说明该材料表现出近似4电子的氧还原反应途径。研究结果表明,WN-W/NOMC的催化性能虽然稍弱于商业铂碳(0.99 V,5.1 mA·cm~(-2)),但其具有远超铂碳的循环稳定性和耐甲醇毒化能力。     

碱性燃料电池Co-N/C复合催化剂的电化学性能

碳黑经过酸处理后再加入醋酸钴经氨气900 ℃热处理后, 以其制备的气体扩散电极在6 mol•L^―1 KOH溶液中对氧还原反应(ORR)的电催化性能得到大大提高. XRD物相分析表明: 碳粉中加入醋酸钴经氨气热处理生成了氮化钴(Co_5.47N). 通过极化曲线和交流阻抗方法对制备的气体扩散电极在空气中的性能进行了研究. 室温时在－0.2 V (vs. Hg/HgO)电位下, 未经处理的碳电极对氧还原基本没有电流产生; 用酸处理后的碳电极在空气中的电流密度提高到57 mA•cm^―2; 而Co-N/C复合电极在同样条件下电流密度可达170 mA•cm^―2, 交流阻抗显示氮化物的生成减小了氧还原反应的阻抗, 增强了对氧还原反应的电催化作用.     

Polyaniline‐Modified Silver and Binary Silver‐Cobalt Catalysts for Oxygen Reduction Reaction

Novel dendrite‐like silver particles were electrodeposited on Ti substrates from a supporting electrolyte‐free 30 mmol L^?1 Ag(NH₃)₂⁺ solution, to synthesize the den‐Ag/Ti electrode. Binary Ag_xCo_y/Ti electrodes with different Ag:Co atomic ratios were further obtained by electrodeposition of Co particles on the den‐Ag/Ti electrode. Polyaniline (PANI) modified den‐Ag/Ti and Ag_xCo_y/Ti electrodes, PANI(n)‐den‐Ag/Ti and PANI(n)‐Ag_xCo_y/Ti, were also obtained by cyclic voltammetry at different numbers of cycles (n) in acidic and alkaline solutions containing aniline, respectively. All these electrodes exhibit high electroactivity for oxygen reduction reaction (ORR) in alkaline solution and their electroactivities follow the order: PANI(15)‐Ag₃₁Co₆₉/Ti>Ag₃₁Co₆₉/Ti>PANI(20)‐den‐Ag/Ti>den‐Ag/Ti. Among them, PANI(15)‐Ag₃₁Co₆₉/Ti displays the highest electrocatalytic activity for ORR with a much positive onset potential of 0 V (vs. Ag/AgCl) and a high ORR current density of 1.2 mA cm^?2 at ?0.12 V (vs. Ag/AgCl). The electrocatalysts are electrochemically insensitive to methanol and ethanol oxidation, and, as cathode electrocatalysts of direct alcohol fuel cells, can resist poisoning by the possible alcohol crossover from the anode.     

High‐Rate Oxygen Electroreduction over Graphitic‐N Species Exposed on 3D Hierarchically Porous Nitrogen‐Doped Carbons

Nitrogen‐doped species (NDs) are theoretically accepted as a determinant of the catalytic activity of metal‐free N‐doped carbon (NC) catalysts for oxygen reduction reaction (ORR). However, direct relationships between ND type and ORR activity have been difficult to extract because the complexity of carbon matrix impairs efforts to expose specific NDs. Herein, we demonstrate the fabrication of a 3D hierarchically porous NC catalyst with micro‐, meso‐, and macroporosity in one structure, in which sufficient exposure and availability of inner‐pore catalytic sites can be achieved due to its super‐high surface area (2191 cm² g^?1) and interconnected pore system. More importantly, in‐situ formation of graphitic‐N species (GNs) on the surface of NC stimulated by KOH activation enables us to experimentally reveal the catalytic nature of GNs for ORR, which is of great significance for the design and development of advanced metal‐free NC electrocatalysts.     

Preparation, Electrochemical Behavior and Electrocatalytic Activity of a Copper Hexacyanoferrate Modified Ceramic Carbon Electrode

A copper hexacyanoferrate modified ceramic carbon electrode （CuHCF/CCE） had been prepared by two-step sol-gel technique and characterized using electrochemical methods. The resulting modified electrode showed a pair of well-defined surface waves in the potential range of 0.40 to 1.0 V with the formal potential of 0.682 V （vs. SCE） in 0.050 mol·dm^-3 HOAc-NaOAc buffer containing 0.30 mol·dm^-3 KCl. The charge transfer coefficient （a） and charge transfer rate constant （ks） for the modified electrode were calculated. The electrocatalytic activity of this modified electrode to hydrazine was also investigated, and chronoamperometry was exploited to conveniently determine the diffusion coefficient （D） of hydrazine in solution and the catalytic rate constant （kcat）. Finally, hydrazine was determined with amperometry using the resulting modified electrode. The calibration plot for hydrazine determination was linear in 3.0 × 10^-6--7.5 × 10^-4 mol·dm^-3 with the detection limit of 8.0 × 10^-7 molodm^-3. This modified electrode had some advantages over the modified film electrodes constructed by the conventional methods, such as renewable surface, good long-term stability, excellent catalytic activity and short response time to hydrazine.     

Electrooxidation of Several Organic Compounds on Simply Prepared Metallic Nanoparticles: A Comparative Study

The electrooxidation of several fuel compounds was studied using metallic nanoparticles of Au, Pd, Pt, AuPd and AuPt synthesized by direct electrodeposition by applying a constant potential of ‐200 mV (vs. Ag/AgCl) to pencil graphite in an acidic medium. Scanning electron microscope (SEM) images and X‐ray diffraction (XRD) data show that monometallic (Au, Pd and Pt) and alloys of bimetallic nanoparticles of AuPd and AuPt have been formed. The catalytic performance of the prepared electrodes was investigated in a neutral medium (100 mM phosphate buffer, pH 7) by cyclic voltammetry. Amongst all fuels, the highest current densities were obtained by the electrooxidation of formic acid (ca. 9.8 mA cm^?2) and formaldehyde (ca. 9.7 mA cm^?2) on the AuPt catalyst.     

Direct electrochemistry of glucose oxidase and sensing glucose using a screen-printed carbon electrode modified with graphite nanosheets and zinc oxide nanoparticles

We have studied the direct electrochemistry of glucose oxidase (GOx) immobilized on electrochemically fabricated graphite nanosheets (GNs) and zinc oxide nanoparticles (ZnO) that were deposited on a screen printed carbon electrode (SPCE). The GNs/ZnO composite was characterized by using scanning electron microscopy and elemental analysis. The GOx immobilized on the modified electrode shows a well-defined redox couple at a formal potential of −0.4 V. The enhanced direct electrochemistry of GOx (compared to electrodes without ZnO or without GNs) indicates a fast electron transfer at this kind of electrode, with a heterogeneous electron transfer rate constant (K_s) of 3.75 s⁻¹. The fast electron transfer is attributed to the high conductivity and large edge plane defects of GNs and good conductivity of ZnO-NPs. The modified electrode displays a linear response to glucose in concentrations from 0.3 to 4.5 mM, and the sensitivity is 30.07 μA mM⁻¹ cm⁻². The sensor exhibits a high selectivity, good repeatability and reproducibility, and long term stability.

Graphical representation for the fabrication of GNs/ZnO composite modified SPCE and the immobilization of GOx