碳载钴酞菁催化剂的一步法制备及其在碱性条件下对氧的电催化还原

通过固相加热,一步合成了以VulcanXC-72(碳黑)为载体的碳载钴酞菁(CoPc/C)复合催化剂,其可用作空气电极的氧还原催化剂。通过X射线衍射、红外光谱等测试技术对催化剂进行了表征。利用极化曲线和交流阻抗(EIS)方法测试了其在碱性介质(6mol/LKOH)中对氧还原的催化性能。结果显示,得到的产物为CoPc/C复合物,平均粒径30nm。以磷酸处理的碳黑为载体,在600℃下制备的CoPc/C复合催化剂表现出最佳的催化活性。以其制备的电极在空气气氛下-0.03V(Hg/HgO)电位时即可产生明显氧还原电流,-0.2V时电流密度达90×10-3A/cm2。     

金属酞菁类大环化合物对氧气还原反应催化行为的阻抗谱研究

通过电化学交流阻抗法研究了3种金属酞菁类大环化合物(FePc, CoPc, FeCoPc2)在碱性溶液中对氧气还原反应(ORR)的电化学催化行为, 各电极的交流阻抗 Nyquist 图谱在高频区和低频区均呈现出2个较明显的半圆和半圆之间(中频区)的压扁的弧形, 采用Zsimpwin阻抗谱分析软件对-02 V(vs. Hg/HgO)电位下的各交流阻抗谱进行等效电路拟合, 提出空气电极ORR反应的等效电路, 并对等效电路中各动力学参数进行了解释, 通过分析得出金属酞菁在碱性溶液中对ORR催化反应是一个伴随中间产物HO-2的2电子转移过程. 同时, 等效电路的拟合结果表明, FeCoPc2/C作为ORR催化剂对减小Rc+Rct效果比FePc/C和CoPc/C明显, 具有更高的催化活性.     

应用于锌-空气电池的新型碳载钴-聚噻吩复合催化剂

采用化学氧化聚合法合成了以碳为载体的钴-聚噻吩复合物(Co-PTh/C)作为气体扩散电极氧还原催化剂。 通过扫描电子显微镜-能量色散X射线能谱（SEM-EDX）、透射电子显微镜（TEM）等测试技术对催化剂进行表征。 结果表明,Co-PTh/C催化剂颗粒的粒径为10~30 nm,且分布均匀。 利用极化曲线、交流阻抗等电化学方法测试了其在碱性介质中(6 mol/L KOH)对氧还原的催化性能。 此催化剂在碱性介质中空气气氛条件下,电极电位在-0.20 V(vs.Hg/HgO)时电流密度达到0.152 A/cm2,催化性能高于质量分数5%Pt/C,显示出优越的氧还原电催化性能。 采取催化层/集流体/扩散层的排布方式,以纯锌为负极,6 mol/L的KOH为电解液,将气体扩散电极与锌负极组装成锌-空气电池。 电池以0.075 A/cm2进行恒流放电,放电电压为1.1 V且性能稳定。     

碱性溶液中空气电极催化剂Co-N/C的研究

采用简单热处理方式制备了空气电极用氧还原电催化剂Co-N/C(800),利用线性电位扫描、控电流极化曲线及单电池测试等方法评价Co-N/C(800)的氧还原反应(ORR)催化活性。结果表明:该催化剂在碱性溶液中(1 mol/LNaOH)对ORR有很好的催化活性,起始氧还原电位约为0.04 V(vs.Hg/HgO);在室温及空气气氛条件下,以Co-N/C(800)制备的空气电极在7 mol/L NaOH溶液中时性能最佳,在电极电位为-0.6 V(vs.Hg/HgO)时电流密度达100 mA/cm2;自制的空气电极与纯锌片所组装的锌-空气电池,以7 mol/L NaOH为电解液,在电池过电位为0.8 V时,电流密度超过了100 mA/cm2,催化性能优于常规MnO2催化剂;同时进行了单电池放电测试,放电平台保持在1.25～1.30 V且性能稳定。     

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.     

有序介孔氮掺杂碳负载三氧化二铁的制备及其催化氧还原性能

制备了有序介孔氮掺杂碳负载三氧化铁,有效降低了氧还原的过电势。通过扫描电子显微镜、透射电子显微镜、氮气吸附-脱附测试、粉末X射线衍射、X射线光电子能谱、拉曼光谱等技术表征了所制备的催化剂的物理化学性质。此外,用旋转圆盘电极测试了其在碱性条件下对氧还原反应的催化活性和选择性。实验结果表明:氮气热解后铁以三氧化二铁的形式负载于有序介孔氮掺杂碳中,其比表面积达到755 cm^2·g^-1。拉曼和X射线光电子能谱结果表明,加入铁前驱体后所制备的催化剂石墨化程度有所提升、阻抗降低、导电性增加。在碱性条件下,Fe2O3@NC催化剂呈现出4电子氧还原反应,其起始电位(-0.01 V vs Ag/AgCl)和半波电位(-0.13 V vs Ag/AgCl)与商用20%Pt/C相当。此外,该催化剂具有较好的抗甲醇性能且其恒电压稳定性优于商用Pt/C。Fe2O3@NC催化剂用于锌-空电池放电测试,其放电功率可以达到88 mW·cm^-2,是商用Pt/C的1.29倍。     

CoPy/C催化剂应用碱性介质氧还原催化的电化学性能

利用碳黑（Vulcan XC-72R）中加入硫酸钴和吡啶（Py）作为催化剂前驱体,经溶剂分散热处理构建了一类新型的高效氧还原CoPy/C复合催化剂.并运用循环伏安法（CV）和旋转圆盘电极（RDE）技术研究了不同Co含量的CoPy/C催化剂在碱性介质中对氧还原的电催化活性.结果表明:Co的存在对氧的催化剂活性位的形成有重要影响,800℃下所制备的10%Co30%Py/C（质量分数）复合催化剂表现出最佳的氧还原催化活性.以其制备的气体扩散电极在3.0 mol·L^-1KOH电解质溶液（O₂气氛）中0.014 V（相对于标准氧电极（RHE））即可产生明显的氧还原电流.同40%Py/C相比,10%Co30%Py/C催化氧还原的起峰电位正移了71 mV,同时表现出明显的极限扩散电流.在-0.16 V时电流密度达到最大值,电流密度为1.0 mA·cm^-2,半波电位在-0.07 V.透射电镜分析表明所制备的碳黑载吡啶钴（10%Co30%Py/C）催化剂平均粒径为20 nm.     

高分散钴氮共掺杂碳纳米纤维氧还原催化剂

过渡金属氮掺杂碳基催化剂已成为替代铂基氧还原反应(ORR)电催化剂的理想选择。本文通过静电纺丝技术制备了高比表面、高度分散的钴原子配位氮掺杂的碳纳米纤维催化剂(Co-N/C)。X射线衍射(XRD)和高分辨率透射电镜(HRTEM)结果证实Co元素高度分散于制备的Co-N/C催化剂中。X射线光电子能谱结果表明N元素主要以吡啶N和石墨N形式存在。该Co-N/C催化剂对ORR反应呈现出较高的电催化活性,其氧还原起始和半波电位分别为0.92 V和0.80 V(相对于标准氢电极),接近于商业化Pt/C催化剂的性能。以制备的Co-N/C催化剂作为阴极,25℃下锌空气燃料电池的开路电位1.54 V、最大功率密度达到了190 m V·cm~(-2)表明该催化剂具有良好的应用前景。     

Fe-N/C-TsOH催化剂应用碱性介质催化氧还原的电催化活性(英文)

通过溶剂分散热处理方法制备了一种吡咯和对甲苯磺酸(TsOH)共同修饰的碳载非贵金属复合催化剂(Fe-N/C-TsOH),并采用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对催化剂的形貌和组成成分进行表征.借助循环伏安法(CV)和旋转圆盘技术研究了TsOH对催化剂在0.1 mol·L-1KOH介质中催化氧还原性能的影响.结果表明:TsOH的存在对催化剂催化氧还原反应(ORR)的活性影响很大.以其制备的气体扩散电极在碱性电解质溶液中催化氧还原过程时转移的电子数为3.899,远比不含TsOH修饰的催化剂催化氧还原的电子数(3.098)高.此外,研究发现600°C热处理过的Fe-N/C-TsOH催化剂表现出最佳的氧还原催化性能.相比未经热处理过的Fe-N/C-TsOH催化剂,起峰电位和-1.5 mA·cm-2电流密度对应的电压分别向正方向移动30和170 mV.XPS研究结果表明吡咯氮是催化剂主要活性中心,提供氧还原活性位,而TsOH加入形成的C―Sn―C和―SOn―有利于催化剂催化氧还原活性的提高,从而使该催化剂对氧还原表现出很好的电催化性能和选择性.     

包覆氮化铁的Fe,N掺杂碳纳米纤维的制备及对氧还原反应的催化性能

通过静电纺丝、碳化和氨气刻蚀制备了具有核-壳结构的包覆氮化铁(FexN)纳米颗粒的Fe,N共掺杂多孔碳纳米纤维(FexN@Fe-N-C),并研究了其在酸性和碱性介质中对氧还原反应(ORR)的电催化性能.结果表明,该催化剂具有优异的氧还原催化活性,在酸性介质中的半波电位(E1/2)可达0. 81 V(vs. RHE),在碱性条件下的E1/2高达0. 897 V,高于商业Pt/C催化剂.在酸性介质中经过10000周加速衰减测试后,FexN@Fe-N-C的E1/2仅衰减了26 m V,展示出极佳的耐久性.离子探针和浓酸刻蚀实验结果表明,Fe-Nx以及FexN纳米颗粒均对ORR有重要催化作用.     

Preparation and Performance of a Novel Bifunctional Catalyst for Autoxidation of Mercaptans

Cobalt phthalocyanine (CoPc) complexes in the presence of caustic are widely used in the refining industry for sweetening (i. e. the catalytic oxidation of mercaptans to disulfides) of petroleum products^[1]. However, the use of caustic leads to the environmental and economic disadvantages because the spent caustic is recognized as a hazardous material. To set up a more environmentally friendly process, Holmgren et al. and Liu et al. recently reported that bifunctional mixed Mg-Al oxide (denoted as Mg(Al)O)-supported CoPc catalysts, which possess oxidation sites and basic sites, can effectively oxidize mercaptans to disulfides^[2,3]. But for these catalysts, we found that the formation of CoPc aggregates on Mg(Al)O during the autoxidation led to their deactivation.³ It is known that the aggregation can be inhibited by anchoring CoPc to supports, such as TiO₂ and SiO₂, modified with organic functional groups. However,it is unknown whether the basic Mg(Al)O materials can be functionalized with organic compounds with no damage to their basic sites. Here we report the preparation of a novel bifunctional catalysts of cobalt tetraaminophthalocyanine CoPc(NH₂)₄ covalently bound to Mg(Al)O modified with a organosilane, as well as their catalytic performance in mercaptan autoxidation.     

吡啶掺杂碳载钴酞菁催化氧还原的电化学性能及在燃料电池中的应用

以碳黑(Vulcan XC-72R)为载体, 吡啶(Py)和钴酞菁(CoPc)为催化剂前驱体, 经溶剂分散法制备了Py掺杂碳负载纳米钴酞菁复合催化剂(Py-CoPc/C). 通过扫描电镜-能谱分析(SEM-EDS)、X射线光电子能谱(XPS)分析和X射线衍射(XRD)分析技术对催化剂的组成和微观结构进行了表征, 并运用线性扫描循环伏安法(LSV)和旋转圆盘电极(RDE)技术考察了不同Py掺杂含量对碳载钴酞菁(CoPc/C)催化氧还原反应(ORR)活性的影响及稳定性. 结果显示: Py掺杂可以明显改善CoPc/C 对ORR的电催化性能, 其中掺杂20%Py下所制备的20%Py-20%CoPc/C 催化剂对ORR表现出最佳的催化活性, 以其制备的气体扩散电极在O₂气氛饱和的0.1 mol·L^-1 KOH 电解质溶液中, 0.2 V (相对于标准氢电极)即可产生明显的氧还原电流, 半波电位为-0.03 V. 相比于40%Py/C 和未掺杂的40%CoPc/C, 20%Py-20%CoPc/C催化剂的半波电位分别正移了160 和15 mV. 进一步运用RDE理论研究表明, 在Py-CoPc/C 电极上ORR的电子转移总数为2.38, 高于CoPc/C电极上的电子转移总数1.96, 从而使ORR的选择性明显提高. SEM-EDS和XRD分析表明Py掺杂提高了CoPc/C催化剂的分散性和N含量, 更利于O₂的吸附. XPS分析表明: 吡啶结构的N与石墨结构的N均存在于Py-CoPc/C 催化剂中,与催化剂表面的Co离子配位可能是促使ORR活性提高的原因. 最后以20%Py-20%CoPc/C制备了膜电极组装(MEA)电极, 应用于H₂/O₂ 燃料电池单电池发电, 室温下获得最大发电功率密度为21 mW·cm^-2, 相对于CoPc/C提高至2.4倍.     

Electronic Configuration Regulation by N-Doped MXenes Boosting Electrocatalytic Performance of Cobalt Phthalocyanine

The precise control of electronic configurations of catalytic sites via molecular engineering is significantly desirable for boosting electrocatalytic activity. We reported a new-type composite electrocatalyst with cobalt phthalocyanine supported on N-doped MXene nanosheets (N-MXene/CoPc) through a self-assembly process. Beneficial from the joint action of N sites participation and axial coordination, N-MXene/CoPc exhibits a high ORR activity with positive onset potential (E_onset=0.98 V vs. RHE) and half-wave potential (E_1/2=0.863 V), which is superior over the pristine CoPc (E_1/2=0.72 V) and the composite with undoped MXene as support (MXene/CoPc, E_1/2=0.771 V). Additionally, N-MXene/CoPc exhibits an excellent durability with only 8.5 % attenuation after 25000 s of continuous i-t test, while a more obvious decay 18.6 % for 20 wt.% Pt/C. This work not merely reported a robust ORR catalyst, but more provides a reasonable design strategy for nonnoble-metal catalysts through catalyst-support interactions.     

CoPc/Al2O3催化剂的制备、表征及其催化氧化性能

用原位合成法,以酸性Al2O3为载体,酞菁类金属大环配合物为活性组分,合成出CoPc/Al2O3新型环氧化催化剂,红外、紫外-可见、热重分析及XPS证实能够利用该法在Al2O3上固载CoPc催化剂,且催化剂稳定性增加,不易流失.以分子氧为氧源,异丁醛为共还原剂考察CoPc/Al2O3催化剂对环己烯的催化环氧化活性及催化剂的重复使用情况.结果表明,与均相催化剂相比,固载后环己烯转化率增加了8%,环氧环己烷选择性增加了23%,催化剂重复使用4次后,活性仅降低4%.     

Cobalt phthalocyanine derivatives supported on TiO2 by sol–gel processing: Part 2. Activity in sulfide and ethanethiol oxidation

The catalytic activity of cobalt(II) 2,9,16,23-tetrasulphophthalocyanine and cobalt(II) 2,9,16,23-tetra(chlorosulphonyl)phthalocyanine covalently bonded to a TiO₂ matrix by sol–gel processing was investigated for sulfide and ethanethiol (CH₃CH₂SH) liquid-phase oxidation. A comparison of the kinetic data as well as the state of active component by using electron spectroscopy in dependence on precursors was carried out. Kinetic data shows that the most stable and active catalysts for ethanethiol oxidation are both CoPc(SO₃H)₄ and CoPc(SO₂Cl)₄ in TiO₂ from Ti(OⁱPr)₄, whereas in the case of Na₂S oxidation in neutral medium the activity of the former is higher.     

Effect of a spacer on phthalocyanine functionalized cellulose nanofiber mats for decolorizing reactive dye wastewater

We report a novel cobalt tetraaminophthalocyanine (CoPc) functionalized nanomaterial by spacer-arm immobilization of CoPc onto cellulose nanofiber mats. The spacer-arm was attached through the reaction of tetraethylenepentamine with oxidized cellulose nanofiber mats. CoPc was then covalently immobilized onto the spacer-arm using glutaraldehyde. The functionalization processes on the nanofiber mats were monitored by attenuated total reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. This CoPc functionalized nanomaterial (CoPc-spacer-NM) was used for decoloration of reactive dye wastewater. Incorporation of the spacer-arm resulted in enhanced decoloration with respect to directly immobilized CoPc onto the cellulose nanofiber mats (CoPc-NM). Compared with CoPc-NM, CoPc-spacer-NM shows much higher adsorption capacity when conducted under acidic conditions, which enhances the catalytic oxidation rate of reactive dye when H₂O₂ was used as an oxidant. Reactive dye wastewater can also be efficiently decolorized by the CoPc-spacer-NM/H₂O₂ system under basic conditions, despite a relatively weak adsorption capacity. Electron paramagnetic resonance results suggested that the catalytic oxidation process involves the formation and reaction of hydroxyl radicals. Gas chromatography–mass spectrometry showed the main products of the catalytic oxidation of reactive red X-3B were biodegradable aliphatic acids, such as oxalic acid, malonic acid and maleic acid.     

Carbon Nanotubes with Phthalocyanine-Decorated Surface Produced by NH3-Assisted Microwave Reaction and Their Catalytic Performance in Li/SOCl2 Battery

Multiwalled carbon nanotube (MWCNT)‐templated cobalt phthalocyanine (CoPc) assemblies are prepared by microwave reaction with the aid of NH₄Cl. The assemblies of CoPc/MWCNTs are added to the electrolyte of Li/SOCl₂ battery to show their potential application in the field of catalysis. The assemblies display a uniform coaxial nanotube structure. In the control test, the CoPc/MWCNTs synthesized without NH₄Cl exhibit the aggregation of the nanotubes of CoPc/MWCNTs. It indicates that the use of NH₄Cl as gas source is efficient in enhancing diffusion of the MWCNTs and controlling the growth of CoPc. The catalytic reduction of SOCl₂ can be carried out by CoPc molecules outside the assemblies and the MWCNTs inside the assemblies. The assemblies of CoPc/ MWCNTs exhibit excellent electrochemical catalytic activity to Li/SOCl₂ battery. The discharge energy of Li/SOCl₂ battery catalyzed by CoPc/MWCNTs is 144% higher than that of the battery without catalyst, and is 94% higher than the energy of Li/SOCl₂ battery catalyzed by bulk CoPc.     

Electrocatalytic Activity of Asymmetrical Cobalt Phthalocyanines in the Presence of N Doped Graphene Quantum Dots: The Push‐pull Effects of Substituents

A series of Co phthalocyanine (CoPc) derivatives and their respective nitrogen doped graphene quantum dot conjugates were used as catalysts towards the electrooxidation of hydrazine. Using a glassy carbon electrode as a support for the electrocatalysts, through cyclic voltammetry and chronoamperometry, the effects of combining the CoPcs with the nitrogen doped graphene quantum dots (NGQDs) were studied. The general observations made were that the NGQDs improve the catalytic activity of the CoPcs in both the π‐π stacked and covalently linked conjugates by increasing the sensitivities and lowering the limits of detection with values as low as 0.43 μM being recorded.     

原位合成法制备TiO2负载酞菁钴催化剂用于CO2光催化还原反应

以钛酸正丁酯为原料采用原位化学合成的新方法,以二价钴离子为模板剂在TiO₂凝胶基质合成的同时,通过邻苯二腈的四聚反应将酞菁钴(CoPc)在TiO₂表面原位合成,得到均匀掺杂的CoPc/TiO₂光催化剂,用紫外-可见漫反射光谱、傅立叶变换-红外光谱等证实了CoPc的成功负载,并将其用于可见光下、水溶液中CO₂的还原反应,通过比较还原反应的效率,确定此光催化剂的最佳制备条件为:CoPc在TiO₂表面的摩尔负载量为3%,焙烧温度为200℃,溶胶搅拌时间为20 h,钛酸丁酯与邻苯二腈及钴离子同时加入溶胶体系中,采用此法制备的催化剂中CoPc酞菁环上的电子密度增加,有利于作为敏化剂的激发态CoPc向半导体TiO₂的导带注入电子,而且CoPc被均匀分散于TiO₂凝胶基质中,其上的“笼效应”有效避免了CoPc的迁移,使其二聚及多聚倾向大大减弱,此光催化剂用于CO₂光还原,在可见光照射下,水溶液中即可光还原CO₂为甲醇、甲醛、甲酸等产物,在光照反应10 h后总产量最高可达2903.83μmol/ g-catal。