直接乙醇燃料电池电催化剂制备及其电化学特性
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摘要
直接乙醇燃料电池(DEFC)作为一种可持续性的便携式电源,对于推动3G时代的发展具有重大意义,能够解决现有便携式电子设备电源连续使用时间短,充电时间长的问题。目前,DEFC的研究处于起步阶段,关键问题在于如何提高催化剂活性,降低成本。以往研究主要集中在对Pt进行改性,如Pt基二元,三元催化剂。Pt表面乙醇电氧化属于结构敏感型反应,受Pt-Pt键键能、d态电子轨道等催化剂表面几何和电子结构的影响。电极表面乙醇电氧化过程是一个三相反应,与传质、反应活性位、电子和质子传输等因素有关。载体对催化剂的性能有很大影响。碳载体对负载的贵金属催化剂的性质如粒子尺寸、形貌、粒径分布、合金化程度、稳定性和分散性等有较大的影响。而且,碳载体也影响负载催化剂在燃料电池中的性能,如质子传输、催化剂层导电性、电化学表面积和金属纳米颗粒的稳定性等,因此有必要对碳载体进行优化。碳载体的性质如比表面积、孔结构、形貌、表面官能团、导电性、防腐性等都必须优化以达到制备高活性催化剂的目的。因此,乙醇电氧化催化剂载体的研究对提高直接乙醇燃料电池的性能至关重要。本文系统地研究了载体的比表面积、孔结构、导电率及载体与活性组分间的相互作用对催化剂活性的影响,针对乙醇电氧化反应特点利用载体的协同作用来提高Pt的催化活性、利用率和寿命,降低成本。
首先,利用Pt直接嵌入溶胶-凝胶法制备可调变粒径和孔结构的低Pt载量Pt/碳干凝胶(CX)催化剂。通过调节pH值制备了一系列比表面积在400m2/g-600m2/g之间,孔径分布从大孔向微孔过渡的Pt/CX-n电催化剂。研究发现,当pH值为7.05时制备的Pt/CX-7.05催化剂具有最佳的乙醇电氧化催化活性, Pt的电化学活性比表面积为134.2m2/g,约为20% Pt/C商业催化剂的1.6倍;Pt利用率可达39.7%。碳干凝胶与Pt之间较强的相互作用,使得CO起始氧化电位比20% Pt/C商业催化剂降低约60mV,增强了抗CO中毒能力。CX较高的石墨化程度明显提高了电导率;其较大的比表面积和发达的介孔结构为乙醇及其中间产物的传递提供了良好的通道,有效提高Pt的利用率。该方法在制备碳干凝胶过程中直接嵌入Pt,利用EDTA有效控制了Pt团聚,避开了传统的先制备碳载体后修饰再负载Pt的工艺。
其次,先以WO3对碳载体进行修饰,制备了Pt/W原子比分别为2.6、5.6和7.5的Ptx/WO3-C电催化剂。实验发现,催化剂对乙醇电氧化催化活性排列如下:Pt5.6/WO3-C > Pt2.6/WO3-C > Pt7.5/WO3-C > 20% Pt/C。Ptx/WO3-C电催化剂降低了乙醇电氧化起始电位,提高了峰值电流密度,具有较高的乙醇电氧化催化活性。这是由于WO3的溢氢效应促进了乙醇及其中间产物在Pt表面的解离吸附;-OHads在WO3表面的低电位形成(又称CO溢出效应),在一定程度上减轻了COads中毒的影响,腾出更多的Pt活性位有利于乙醇电氧化反应的进行。WO3对Pt的电子调变作用,使得Ptx/WO3-C电催化剂中Pt的晶格参数增大,有利于乙醇的吸附脱氢,同时还削弱了Pt-CO键键能,降低了CO氧化电位。Ptx/WO3-C电催化剂的催化活性并不随着WO3的含量增加而提高,这是由于WO3对Pt的协同作用发生在两者的相邻界面上,因此受WO3和Pt颗粒大小及分散度的影响。
第三,系统地研究了单壁碳纳米管(SWNT)负载Pt基催化剂在DEFC中的性能。分别以H2O2、HNO3、H2SO4+HNO3混酸对SWNT进行预处理,研究了预处理方式对SWNT及相应的负载Pt催化剂性能的影响。实验发现,经HNO3处理后的SWNT-N中原本卷曲缠绕的SWNT被拉直,杂质及非晶碳减少,比表面积为255.4m2/g,比原始SWNT略有减少,平均孔径在7nm左右。相应的Pt/SWNT-N催化剂对乙醇氧化电催化活性最佳。经H2O2处理后的SWNT-O,虽然比表面积更大(401.4 m2/g),平均孔径也为7nm,但其单位质量Pt的电化学活性面积和Pt利用率均比Pt/SWNT-N催化剂小。这与SWNT-O管子弯曲缠绕,表面结构缺陷多有关。SWNT负载Pt催化剂中的Pt晶格参数比20% Pt/C商业催化剂的小,不利于乙醇的吸附脱氢,且SWNT表面结构缺陷越多,负载的Pt晶格参数越小。但SWNT本身具有吸附氢物种的性能,因此弥补了这一不足。
此外,还系统地比较SWNT、MWNT及VulcanXC-72炭黑为载体的负载型Pt催化剂。比较发现,MWNT由于具有多层石墨管状结构,结构缺陷多、比表面积小,使得负载的Pt平均粒径比SWNT上的大,且晶格参数更小,因此不利于氢和乙醇的吸附脱氢;部分Pt沉积在MWNT的内壁,但由于管口被Pt阻塞,导致整体Pt利用率降低。此外还利用Sn修饰制备了PtSn/SWNT电催化剂。研究发现:Sn在催化剂中以合金态和氧化态两种形式存在,前者使Pt晶格扩张,有利于乙醇及其中间产物的吸附氧化;后者能在较低电位下吸附-OHads,促进CO的氧化,增强催化剂的抗中毒能力。但SnOx是不良导体,过多添加Sn会降低催化剂导电率;且SnOx的耐腐蚀性低。
最后,探索性研究了非贵金属Mo2C/C电催化剂。研究发现,Mo2C/C不仅具有氢的电催化氧化活性且具有氧还原电催化活性,证明Mo2C具有类Pt催化性能。XRD、TEM和XPS分析表明,Mo2C/C催化剂体相为β-Mo2C,表相存在MoOxCy和MoOz物种。MoOxCy和MoOz的氧化还原以及氧在β-Mo2C晶格中的迁移是其催化活性的根源。
As a sustained portable power supply, direct ethanol fuel cell (DEFC) plays a significant role in promoting the development of 3G era. It can resolve some problems of portable electronic devices, such as limited continuous working time and long charging time. At present, the DEFC research just starts, the key problem is how to improve catalyst activity and reduce cost. Researchers used to focus on the Pt modification. Binary and ternary Pt-based catalysts have been systematically studied. Ethanol electrooxidation on Pt is a structure-sensitive reaction. It is influenced by the catalyst surface geometry and electronic structure, such as the Pt-Pt bond energy, d-state electronic orbital. Ethanol electrooxidation on electrode surface is a three-phase reaction, affected by combined factors of the mass transfer, reaction active site, electron and proton transfer. In this paper, we focus on supporting materials, systematically study the interaction between support and metal in order to choose suitable catalyst support for the ethanol electrooxidation. The support-metal interaction may help to improve the activity and utility of Pt, reduce the cost.
First, Pt embedded carbon xerogel catalysts are prepared by sol-gel method. By adjusting the pH value, we could vary carbon particle size and pore size distribution. A series of differ surface area (400 m2/g-600 m2/g) catalysts are prepared. Their pore size distribution varies from macro pore to micro pore. When the pH value is 7.05, as prepared Pt/CX-7.05 catalyst has the best catalytic activity for ethanol electrooxidation. Its Pt utilization reachs 39.7%, which is more than 4 times than that of the 20% Pt/C commercial catalyst. Its electrochemical surface area of Pt is 134.2m2/g, about 1.6 times than that of the 20% Pt/C commercial catalyst. The strong interaction between carbon xerogel and Pt of Pt/CX-7.05 catalyst makes its CO oxidation onset potential lower about 60mV than that of the 20% Pt/C commercial catalyst, enhances its CO-tolerance. The large surface area and mesoporous structure of Pt/CX-7.05 catalyst is good for the transmission of ethanol and intermediates, and efficiently improves the Pt utilization. The high graphitization of carbon xerogel increases the catalyst conductivity. In addition, this method directly embeds Pt in carbon during the carbon xerogel preparation, avoiding the traditional cumbersome process (make carbon, then modified, and Pt loading). The use of EDTA could effectively protect Pt from agglomerating.
Secondly, WO3 modified VulcanXC-72 is used as composite support to prepare a series of Ptx/WO3-C catalysts, the atomic rate of Pt and W varies from 2.6:1,5.6:1 to 7.5:1. We find that WO3 not only has the―hydrogen spillover‖effect, but also has electronic modulation effect on Pt. The Pt lattice constants of the Ptx/WO3-C catalysts are enlarged, which is good for ethanol adsorption and dehydrogenation. It also weakens the Pt-CO bond, lowering the onset potential of the CO electrooxidation reaction. The Pt5.6/WO3-C catalyst shows the highest catalytic activity. Because the synergetic effect between WO3 and Pt occurs on their adjacent interface, it is affected by the distribution and size of the WO3 and Pt particles.
We systematically study the performance of SWNT supported Pt-based catalysts in DEFC. SWNTs are pretreated by H2O2, HNO3 and the mixture acid (made of H2SO4 and HNO3), respectively. The effect of differ pretreatments is studied. After treated by HNO3, the winding original SWNT is straightened, its surface area decreases slightly from 292.0m2/g to 255.4m2/g, and its average pore size decreases to 7nm. As prepared Pt/SWNT-N catalyst has the best electrocatalytic activity for the ethanol oxidation reaction. The SWNT-O, treated by H2O2, has the largest surface area (401.4m2/g). Its average pore size is around 7nm. But the EAS of the Pt/SWNT-O catalyst is smaller than that of the Pt/SWNT-N catalyst. Because SWNT-O has more winding tubes, which means SWNT-O has more structure defects than SWNT-N. The Pt lattice constants of the SWNT supported Pt catalysts are smaller than that of the 20% Pt/C commercial catalyst, which is unfavorable for the hydrogen and ethanol absorption. However, the SWNT itself could adsorb hydrogen species, so to make up for the shortage.
Additionally, SWNT-N, MWNT-N and VulcanXC-72 supported Pt catalysts are compared. We find the Pt/SWNT-N catalyst has the highest catalytic activity, and the Pt/MWNT-N catalyst has the lowest. Because MWNT-N has lots of structure defects and its surface area only is 49.7m2/g. Some Pt particles are deposited on the inner wall of the MWNT-N and blocked by the Pt particles loading on the tube mouth. The addition of Sn in Pt/SWNT-N is studied as well. There are both alloyed and oxidized Sn in PtSn/SWNT-N catalyst. The alloyed Sn enlarged the Pt lattice constant, which could improve the ethanol adsorption and weaken the Pt-CO bond. The Sn oxides adsorb–OHads at low potential, which would accelerate the oxidation of COads and improve the CO-tolerance. However, the SnOx are insulator. Too much addition of Sn would increase the resistance. Worse, SnOx has low corrosion resistance.
Mo2C/C is used as oxygen reduction electrocatalyst for PEM fuel cell. The electrocatalytic activity for oxygen reduction is evaluated by single cell testing and cyclic voltammetry technique. Combined with the results gained by X-ray diffraction and X-ray photoelectron spectroscopy, respectively, its electrocatalytic mechanism is primarily analyzed. Mo2C/VC has electrocatalytic activity for oxygen reduction. The catalytic activity should be contributed to the redox of surface passivated species (MoOxCy and MoOz) and the oxygen migration in the crystal lattice of bulkβ- Mo2C.
首先,利用Pt直接嵌入溶胶-凝胶法制备可调变粒径和孔结构的低Pt载量Pt/碳干凝胶(CX)催化剂。通过调节pH值制备了一系列比表面积在400m2/g-600m2/g之间,孔径分布从大孔向微孔过渡的Pt/CX-n电催化剂。研究发现,当pH值为7.05时制备的Pt/CX-7.05催化剂具有最佳的乙醇电氧化催化活性, Pt的电化学活性比表面积为134.2m2/g,约为20% Pt/C商业催化剂的1.6倍;Pt利用率可达39.7%。碳干凝胶与Pt之间较强的相互作用,使得CO起始氧化电位比20% Pt/C商业催化剂降低约60mV,增强了抗CO中毒能力。CX较高的石墨化程度明显提高了电导率;其较大的比表面积和发达的介孔结构为乙醇及其中间产物的传递提供了良好的通道,有效提高Pt的利用率。该方法在制备碳干凝胶过程中直接嵌入Pt,利用EDTA有效控制了Pt团聚,避开了传统的先制备碳载体后修饰再负载Pt的工艺。
其次,先以WO3对碳载体进行修饰,制备了Pt/W原子比分别为2.6、5.6和7.5的Ptx/WO3-C电催化剂。实验发现,催化剂对乙醇电氧化催化活性排列如下:Pt5.6/WO3-C > Pt2.6/WO3-C > Pt7.5/WO3-C > 20% Pt/C。Ptx/WO3-C电催化剂降低了乙醇电氧化起始电位,提高了峰值电流密度,具有较高的乙醇电氧化催化活性。这是由于WO3的溢氢效应促进了乙醇及其中间产物在Pt表面的解离吸附;-OHads在WO3表面的低电位形成(又称CO溢出效应),在一定程度上减轻了COads中毒的影响,腾出更多的Pt活性位有利于乙醇电氧化反应的进行。WO3对Pt的电子调变作用,使得Ptx/WO3-C电催化剂中Pt的晶格参数增大,有利于乙醇的吸附脱氢,同时还削弱了Pt-CO键键能,降低了CO氧化电位。Ptx/WO3-C电催化剂的催化活性并不随着WO3的含量增加而提高,这是由于WO3对Pt的协同作用发生在两者的相邻界面上,因此受WO3和Pt颗粒大小及分散度的影响。
第三,系统地研究了单壁碳纳米管(SWNT)负载Pt基催化剂在DEFC中的性能。分别以H2O2、HNO3、H2SO4+HNO3混酸对SWNT进行预处理,研究了预处理方式对SWNT及相应的负载Pt催化剂性能的影响。实验发现,经HNO3处理后的SWNT-N中原本卷曲缠绕的SWNT被拉直,杂质及非晶碳减少,比表面积为255.4m2/g,比原始SWNT略有减少,平均孔径在7nm左右。相应的Pt/SWNT-N催化剂对乙醇氧化电催化活性最佳。经H2O2处理后的SWNT-O,虽然比表面积更大(401.4 m2/g),平均孔径也为7nm,但其单位质量Pt的电化学活性面积和Pt利用率均比Pt/SWNT-N催化剂小。这与SWNT-O管子弯曲缠绕,表面结构缺陷多有关。SWNT负载Pt催化剂中的Pt晶格参数比20% Pt/C商业催化剂的小,不利于乙醇的吸附脱氢,且SWNT表面结构缺陷越多,负载的Pt晶格参数越小。但SWNT本身具有吸附氢物种的性能,因此弥补了这一不足。
此外,还系统地比较SWNT、MWNT及VulcanXC-72炭黑为载体的负载型Pt催化剂。比较发现,MWNT由于具有多层石墨管状结构,结构缺陷多、比表面积小,使得负载的Pt平均粒径比SWNT上的大,且晶格参数更小,因此不利于氢和乙醇的吸附脱氢;部分Pt沉积在MWNT的内壁,但由于管口被Pt阻塞,导致整体Pt利用率降低。此外还利用Sn修饰制备了PtSn/SWNT电催化剂。研究发现:Sn在催化剂中以合金态和氧化态两种形式存在,前者使Pt晶格扩张,有利于乙醇及其中间产物的吸附氧化;后者能在较低电位下吸附-OHads,促进CO的氧化,增强催化剂的抗中毒能力。但SnOx是不良导体,过多添加Sn会降低催化剂导电率;且SnOx的耐腐蚀性低。
最后,探索性研究了非贵金属Mo2C/C电催化剂。研究发现,Mo2C/C不仅具有氢的电催化氧化活性且具有氧还原电催化活性,证明Mo2C具有类Pt催化性能。XRD、TEM和XPS分析表明,Mo2C/C催化剂体相为β-Mo2C,表相存在MoOxCy和MoOz物种。MoOxCy和MoOz的氧化还原以及氧在β-Mo2C晶格中的迁移是其催化活性的根源。
As a sustained portable power supply, direct ethanol fuel cell (DEFC) plays a significant role in promoting the development of 3G era. It can resolve some problems of portable electronic devices, such as limited continuous working time and long charging time. At present, the DEFC research just starts, the key problem is how to improve catalyst activity and reduce cost. Researchers used to focus on the Pt modification. Binary and ternary Pt-based catalysts have been systematically studied. Ethanol electrooxidation on Pt is a structure-sensitive reaction. It is influenced by the catalyst surface geometry and electronic structure, such as the Pt-Pt bond energy, d-state electronic orbital. Ethanol electrooxidation on electrode surface is a three-phase reaction, affected by combined factors of the mass transfer, reaction active site, electron and proton transfer. In this paper, we focus on supporting materials, systematically study the interaction between support and metal in order to choose suitable catalyst support for the ethanol electrooxidation. The support-metal interaction may help to improve the activity and utility of Pt, reduce the cost.
First, Pt embedded carbon xerogel catalysts are prepared by sol-gel method. By adjusting the pH value, we could vary carbon particle size and pore size distribution. A series of differ surface area (400 m2/g-600 m2/g) catalysts are prepared. Their pore size distribution varies from macro pore to micro pore. When the pH value is 7.05, as prepared Pt/CX-7.05 catalyst has the best catalytic activity for ethanol electrooxidation. Its Pt utilization reachs 39.7%, which is more than 4 times than that of the 20% Pt/C commercial catalyst. Its electrochemical surface area of Pt is 134.2m2/g, about 1.6 times than that of the 20% Pt/C commercial catalyst. The strong interaction between carbon xerogel and Pt of Pt/CX-7.05 catalyst makes its CO oxidation onset potential lower about 60mV than that of the 20% Pt/C commercial catalyst, enhances its CO-tolerance. The large surface area and mesoporous structure of Pt/CX-7.05 catalyst is good for the transmission of ethanol and intermediates, and efficiently improves the Pt utilization. The high graphitization of carbon xerogel increases the catalyst conductivity. In addition, this method directly embeds Pt in carbon during the carbon xerogel preparation, avoiding the traditional cumbersome process (make carbon, then modified, and Pt loading). The use of EDTA could effectively protect Pt from agglomerating.
Secondly, WO3 modified VulcanXC-72 is used as composite support to prepare a series of Ptx/WO3-C catalysts, the atomic rate of Pt and W varies from 2.6:1,5.6:1 to 7.5:1. We find that WO3 not only has the―hydrogen spillover‖effect, but also has electronic modulation effect on Pt. The Pt lattice constants of the Ptx/WO3-C catalysts are enlarged, which is good for ethanol adsorption and dehydrogenation. It also weakens the Pt-CO bond, lowering the onset potential of the CO electrooxidation reaction. The Pt5.6/WO3-C catalyst shows the highest catalytic activity. Because the synergetic effect between WO3 and Pt occurs on their adjacent interface, it is affected by the distribution and size of the WO3 and Pt particles.
We systematically study the performance of SWNT supported Pt-based catalysts in DEFC. SWNTs are pretreated by H2O2, HNO3 and the mixture acid (made of H2SO4 and HNO3), respectively. The effect of differ pretreatments is studied. After treated by HNO3, the winding original SWNT is straightened, its surface area decreases slightly from 292.0m2/g to 255.4m2/g, and its average pore size decreases to 7nm. As prepared Pt/SWNT-N catalyst has the best electrocatalytic activity for the ethanol oxidation reaction. The SWNT-O, treated by H2O2, has the largest surface area (401.4m2/g). Its average pore size is around 7nm. But the EAS of the Pt/SWNT-O catalyst is smaller than that of the Pt/SWNT-N catalyst. Because SWNT-O has more winding tubes, which means SWNT-O has more structure defects than SWNT-N. The Pt lattice constants of the SWNT supported Pt catalysts are smaller than that of the 20% Pt/C commercial catalyst, which is unfavorable for the hydrogen and ethanol absorption. However, the SWNT itself could adsorb hydrogen species, so to make up for the shortage.
Additionally, SWNT-N, MWNT-N and VulcanXC-72 supported Pt catalysts are compared. We find the Pt/SWNT-N catalyst has the highest catalytic activity, and the Pt/MWNT-N catalyst has the lowest. Because MWNT-N has lots of structure defects and its surface area only is 49.7m2/g. Some Pt particles are deposited on the inner wall of the MWNT-N and blocked by the Pt particles loading on the tube mouth. The addition of Sn in Pt/SWNT-N is studied as well. There are both alloyed and oxidized Sn in PtSn/SWNT-N catalyst. The alloyed Sn enlarged the Pt lattice constant, which could improve the ethanol adsorption and weaken the Pt-CO bond. The Sn oxides adsorb–OHads at low potential, which would accelerate the oxidation of COads and improve the CO-tolerance. However, the SnOx are insulator. Too much addition of Sn would increase the resistance. Worse, SnOx has low corrosion resistance.
Mo2C/C is used as oxygen reduction electrocatalyst for PEM fuel cell. The electrocatalytic activity for oxygen reduction is evaluated by single cell testing and cyclic voltammetry technique. Combined with the results gained by X-ray diffraction and X-ray photoelectron spectroscopy, respectively, its electrocatalytic mechanism is primarily analyzed. Mo2C/VC has electrocatalytic activity for oxygen reduction. The catalytic activity should be contributed to the redox of surface passivated species (MoOxCy and MoOz) and the oxygen migration in the crystal lattice of bulkβ- Mo2C.
引文
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