CN109666949A - 多元掺杂的活性炭电极的制备方法、活性炭催化剂的表征和氧还原电催化测试方法 - Google Patents
多元掺杂的活性炭电极的制备方法、活性炭催化剂的表征和氧还原电催化测试方法 Download PDFInfo
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Abstract
本发明涉及电化学合成领域,特别涉及一种钴氧化物和氮掺杂的介孔活性炭电极的制备方法,包括:⑴一锅法制备以介孔活性炭为基体的催化剂前体;⑵退火合成多元掺杂的活性炭催化剂;⑶制备电极膜凝胶并辊压呈电极膜;⑷将两片电极膜辊压在集流体上,最终形成“三明治”结构的电极。本发明所述的方法简单,易操作。依照本发明制作的电极表面分布大量的介孔结构,提供了氧还原的催化位点;同时由于氮和钴氧化物的掺杂使得电极表面催化位点上氧气及自由基的吸附能垒降低,加速电极表面氧气的还原;此外由于钴氧化物的掺杂加强氧还原反应的二电子过程的选择性,电解合成双氧水的电流效率极高。
Description
技术领域
本发明涉及电催化合成领域,特别涉及一种多元掺杂活性炭电极的制备方法、活性炭催化剂的表征和氧化还原电催化测试方法。
背景技术
双氧水在化工合成以及环境处理领域有着重要的作用。然而现在双氧水的合成方法主要是蒽醌法以及氢氧直接合成法,这些方法存在着技术复杂、合成能耗高、化学药剂消耗大、存在安全隐患等诸多问题。电合成双氧水通过电解过程中阴极发生的氧还原反应,将电解液中的氧气还原成双氧水,其合成方法和条件简单、能耗低、化学药剂消耗少、安全隐患小等诸多优点,是最具前景的双氧水合成方法。
然而,氧还原反应分为四电子传递和二电子传递两个不同的过程,其中二电子传递过程中,氧气最终被还原成双氧水,而四电子传递过程中氧气最终被还原成水。电极材料是影响氧还原反应电子传递选择性的关键,其中碳基材料具有廉价、稳定性强等优点,是最合适的电极基材。通过对碳基材料进行掺氮处理可以形成石墨氮、吡咯氮和吡啶氮的结构,其可以增强谈及材料的电导率以及增强碳基材料上的活性位点对氧及自由基的吸附。此外,在碳基材料负载过度金属及过度金属氧化物可以有效改变活性位点对氧气及自由基的吸脱附活化能,进而改变氧还原过程的电子传递选择性。
发明内容
本发明的目的是提供一种针对当今电合成双氧水领域中电流效率低的问题,开发一种廉价的多元掺杂活性炭电极。本发明的另一目的是提供一种制作方法简单、电解效果稳定、双氧水合成电流效率高、使用寿命长的多元掺杂活性炭电极的制备方法。
本发明的技术解决方案是所述多元掺杂活性炭电极的制备方法,其特殊之处在于,包括以下步骤:
⑴将介孔活性炭、二价钴盐和三聚氰胺进行混合,一锅法制备以介孔活性炭为基体的催化剂前体;
⑵将步骤⑴得到的产物通过退火,合成多元掺杂活性炭催化剂 (CoOx@N-AC);
⑶将步骤⑵得到的CoOx@N-AC与导电剂、PTFE乳液和无水乙醇进行混合、超声分散,配制成电极膜凝胶;
⑷将步骤⑶合成的电极膜凝胶辊压呈电极膜;
⑸将两片步骤⑷得到的电极膜辊压在集流体的两侧,形成“三明治”结构的电极。
作为优选:所述介孔活性炭的平均粒径为45~150μm;所述介孔活性炭的介孔分布为5~30nm。
作为优选:所述步骤⑴中活性炭电极,包括以下重量份的组分:
介孔活性炭100 二价钴盐20~60 三聚氰胺20~60。
作为优选:所述二价钴盐为Co(NO3)2·6H2O或(CH3CO2)2Co。
作为优选:所述步骤⑵的退火温度为500~800℃;所述步骤⑵的 CoOx@N-AC、纳米导电炭黑和PTFE的质量比为8:1:1。
作为优选:所述步骤⑶的电极膜凝胶,包括以下重量份的组分:
CoOx@N-AC 100 导电剂 20 PTFE 10。
电极膜凝胶的配制:取5g CoOx@N-AC,1g乙炔炭黑分散于30ml无水乙醇中,超声分散1h,后逐滴加入0.5mlPTFE乳液(30%),边加边搅拌,后继续超声分散1h,后将溶液置于60℃烘箱中将酒精部分烘干,制成电极膜凝胶。
电极的辊压成型:将电极膜凝胶揉成团状,置于辊压机中滚压,对辊间距为0.2mm,多次辊压后得到0.3-0.4mm厚的电极膜;取相应大小的钛网(60目)作为集流体,将两个电极片包覆在钛网的两面,呈“三明治”结构,后置于辊压机中滚压,对辊间距为0.3mm,多次辊压后得到0.55~0.65mm 厚的电极。
所述导电剂为乙炔炭黑、石墨烯、碳纳米管、黑磷、Ti4O7的一种。
作为优选:所述步骤⑶的电极膜的厚度为0.3~0.5mm。
作为优选:所述步骤⑸的集流体为不锈钢网或钛网;辊压制作而成的电极的厚度为0.5~0.8mm。
本发明的另一技术解决方案是所述多元掺杂催化剂(CoOx@N-AC)的表征和氧还原电催化测试方法,其特殊之处在于,包括以下步骤:
⑴称取设定量的活性炭粉末,通过比表面积测定仪测定介孔活性炭的氮气吸附曲线并计算活介孔性炭的比表面积,介孔活性炭的比表面积为 1397.82m2/g,通过Barett-Joyner-Halenda(BJH)算法计算介孔活性炭的孔径分布,介孔活性碳的孔径分布为5~15nm;
⑵取设定量的CoOx@N-AC,通过X射线衍射仪测定CoOx@N-AC中的晶体结构,CoOx@N-AC中钴氧化物以CoO的晶体形态掺杂在介孔活性炭上;
⑶取设定量的CoOx@N-AC,通过X射线光电子能谱仪测定CoOx@N-AC中的元素组成和价态分布,CoOx@N-AC中的氮掺杂以石墨氮为主,Co元素中的 2+的价态更多;
⑷取20mg CoOx@N-AC和2mg乙炔碳黑置于5ml无水乙醇中,加入10 μl Nafion膜溶液,超声分散20min,后取10μl均匀涂覆于玻碳电极上,干燥后置于旋转圆环电极设备中,电解液的pH为3的0.5M Na2SO4溶液,在氧气饱和的条件下采用电化学工作站进行极化曲线的测定,扫描范围为0.2 V(vs.Ag/AgCl)至-0.8V(vs.Ag/AgCl),电极转速为1600rpm;
⑸根据下述公式1和公式2分别计算电子转移数和双氧水得率,求得 CoOx@N-AC的电子转移数和双氧水得率分别为2.4和67.35%,证明CoOx@N-AC 具有极高的氧还原二电子传递选择性:
其中Id和Ir分别是盘电流和环电流(A),N是收集效率N=0.37。
作为优选:所述步骤⑷进一步包括:以铂片(1cm*1cm)为阳极,以电极 (1cm*1cm)为阴极,电解液为pH为3的0.5M Na2SO4电解液,在氧气饱和的条件下采用电化学工作站测定电极的Tafel曲线,扫描范围为开路电压±0.1V;以铂片(1cm*1cm)为阳极,以电极(1cm*1cm)为阴极,中间以阳离子交换膜相隔,电解液为pH为3的0.5M Na2SO4电解液,在氧气饱和的条件下以恒电流模式(10mA/cm2)电解1h,后采用草酸钛钾法测定电解液中双氧水的含量,并通过公式3计算得到电合成双氧水的电流效率,所述电极的双氧水产率为2.36±0.25,电合成双氧水的电流效率为63.25%;
其中n是电子转移数,V是电解液的体积(L),Q是电解过程的电量(C)。
与现有技术相比,本发明的有益效果:
⑴本发明电极选择的材料的成本低廉,实施方法所需条件容易实现、操作简单,具有极高的性价比;
⑵本发明优选了活性炭的介孔孔径分布,优选后的活性炭在后续的掺氮和钴氧化物掺杂过程中具有定向催化的作用,进而增强催化剂和电极的催化活性和氧还原二电子传递的选择性;
⑶本发明通过优选多元掺杂过程中三聚氰胺和二价钴盐的用量,优选退火温度和退火时间,进而定向优选氮和钴氧化物的掺杂形态和晶体构成,进而极大增强了催化剂和电极的氧还原二电子传递的选择性;
⑷本发明通过优选电极合成过程中导电剂和PTFE的用量以及成膜后电极膜的厚度,增强了电极的导电性和机械强度;
⑸本发明电极具有较好的机械强度,具有很强的催化稳定性和环境耐性,具有较好的使用寿命。
附图说明
图1为本发明介孔活性炭的氮气吸附曲线图;
图2为本发明介孔活性炭的孔径分布图;
图3为本发明CoOx@N-AC的X射线衍射图谱;
图4为本发明CoOx@N-AC的X射线光电子能谱图;
图5为本发明CoOx@N-AC中C 1s的X射线光电子能谱图;
图6为本发明CoOx@N-AC中N 1s的X射线光电子能谱图;
图7为本发明CoOx@N-AC中Co 2p的X射线光电子能谱图;
图8为本发明CoOx@N-AC在0.1M H2SO4电解液中,氧气饱和条件下的RRDE极化曲线图;
图9为本发明电极的实物图;
图10为本发明电极在pH为3的0.5M Na2SO4电解液中,氧气饱和条件下的Tafel曲线图。
具体实施方式
本发明下面将结合实施例作进一步详述:
1.CoOx@N-AC的合成:
取10g 200目的介孔活性炭,5gCo(NO3)2·6H2O和4g三聚氰胺,分散于 300ml去离子水中,超声分散4h,后放置于80℃的烘箱中,直至去离子水全部烘干,后置于真空分散机中分散30分钟;将分散好的混合粉末置于马弗炉中,在氮气气氛下以5℃/min升高至800℃,在800℃退火2h后自然冷却至室温,即获得CoOx@N-AC。
2.CoOx@N-AC的表征和氧还原电催化测试:
称取一定量的活性炭粉末,通过比表面积测定仪(M/s,Quantachrome USA)测定介孔活性炭的氮气吸附曲线并计算活介孔性炭的比表面积,介孔活性炭的比表面积为1397.82m2/g;通过Barett-Joyner-Halenda(BJH)算法计算介孔活性炭的孔径分布,介孔活性碳的孔径分布为5-15nm;取一定量的CoOx@N-AC,通过X射线衍射仪(Ultima IV,RigakuCo.Ltd.,Japan)测定CoOx@N-AC中钴氧化物的晶体结构,发现CoOx@N-AC中钴氧化物主要以CoO 的晶体形态掺杂在介孔活性炭上;取一定量的CoOx@N-AC,通过X射线光电子能谱仪(Thermo Fisher Scientific,Rockford,IL)测定CoOx@N-AC中的元素组成和价态分布,发现CoOx@N-AC中的氮掺杂主要以石墨氮为主,Co 元素中的2+的价态更多;取20mg CoOx@N-AC和2mg碳乙炔黑置于5ml无水乙醇中,加入10μlNafion膜溶液,超声分散20min,后取10μl均匀涂覆于玻碳电极上,干燥后置于旋转圆环电极设备中(RRDE-3A,ALS Co.Ltd., Tokyo,Japan),电解液为pH为3的0.5M Na2SO4溶液,在氧气饱和的条件下采用电化学工作站(CHI760D,Chenhua Instrument Co.Ltd.,Shanghai, China)进行极化曲线的测定,扫描范围为0.2V(vs.Ag/AgCl)至 -0.8V(vs.Ag/AgCl),电极转速为1600rpm,根据公式1和公式2分别计算电子转移数和双氧水得率,求得CoOx@N-AC的电子转移数和双氧水得率分别为2.4和67.35%,证明CoOx@N-AC具有极高的氧还原二电子传递选择性。
其中Id和Ir分别是盘电流和环电流(A),N是收集效率N=0.37。
3.电极膜凝胶的配制:
取5gCoOx@N-AC,1g乙炔炭黑分散于30ml无水乙醇中,超声分散1h,后逐滴加入0.5ml PTFE乳液(30%),边加边搅拌,后继续超声分散1h,后将溶液置于60℃烘箱中将酒精部分烘干,制成电极膜凝胶。
4.电极的辊压成型:
将电极膜凝胶揉成团状,置于辊压机中滚压,对辊间距为0.2mm,多次辊压后得到0.3-0.4mm厚的电极膜;取相应大小的钛网(60目)作为集流体,将两个电极片包覆在钛网的两面,呈“三明治”结构,后置于辊压机中滚压,对辊间距为0.3mm,多次辊压后得到0.55-0.65mm厚的电极。
5.电极的电化学活性和双氧水产率和电流效率:
以铂片(1cm*1cm)为阳极,本发明的电极((1cm*1cm))为阴极,电解液为 pH为3的0.5M Na2SO4电解液,在氧气饱和的条件下采用电化学工作站 (CHI760D,ChenhuaInstrument Co.Ltd.,Shanghai,China)测定电极的 Tafel曲线,扫描范围为开路电压±0.1V;以铂片(1cm*1cm)为阳极,本发明的电极(1cm*1cm)为阴极,中间以阳离子交换膜相隔,电解液为pH为3 的0.5M Na2SO4电解液,在在氧气饱和的条件下以恒电流模式(10mA/cm2) 电解1h,后采用草酸钛钾法测定电解液中双氧水的含量,并通过公式3计算得到电合成双氧水的电流效率,本发明的电极的双氧水产率为 2.36±0.25,电合成双氧水的电流效率为63.25%。
其中n是电子转移数,V是电解液的体积(L),Q是电解过程的电量(C)。
以上所述仅为本发明的较佳实施例,凡依本发明权利要求范围所做的均等变化与修饰,皆应属本发明权利要求的涵盖范围。
Claims (10)
1.一种多元掺杂的活性炭电极的制备方法,其特征在于,包括以下步骤:
⑴将介孔活性炭、二价钴盐和三聚氰胺进行混合,一锅法制备以介孔活性炭为基体的催化剂前体;
⑵将步骤⑴得到的产物通过退火,合成多元掺杂活性炭催化剂(CoOx@N-AC);
⑶将步骤⑵得到的CoOx@N-AC与导电剂、PTFE乳液和无水乙醇进行混合、超声分散,配制成电极膜凝胶;
⑷将步骤⑶合成的电极膜凝胶辊压呈电极膜;
⑸将两片步骤⑷得到的电极膜辊压在集流体的两侧,形成“三明治”结构的电极。
2.根据权利要求1所述多元掺杂活性炭电极的制备方法,其特征在于,所述介孔活性炭的平均粒径为45~150μm;所述介孔活性炭的介孔分布为5~30nm。
3.根据权利要求1所述多元掺杂活性炭电极的制备方法,其特征在于,所述步骤⑴中活性炭电极,包括以下重量份的组分:
介孔活性炭100 二价钴盐20~60 三聚氰胺20~60。
4.根据权利要求3所述多元掺杂活性炭电极的制备方法,其特征在于,所述二价钴盐为Co(NO3)2·6H2O或(CH3CO2)2Co。
5.根据权利要求1所述多元掺杂活性炭电极的制备方法,其特征在于,所述步骤⑵的退火温度为500~800℃。
6.根据权利要求1所述多元掺杂活性炭电极的制备方法,其特征在于,所述步骤⑶的电极膜凝胶,包括以下重量份的组分:
CoOx@N-AC 100 导电剂 20 PTFE 10;
电极膜凝胶的配制:取5g CoOx@N-AC,1g乙炔炭黑分散于30ml无水乙醇中,超声分散1h,后逐滴加入0.5mlPTFE乳液(30%),边加边搅拌,后继续超声分散1h,后将溶液置于60℃烘箱中将酒精部分烘干,制成电极膜凝胶;
电极的辊压成型:将电极膜凝胶揉成团状,置于辊压机中辊压,对辊间距为0.2mm,多次辊压后得到0.3~0.4mm厚的电极膜;取相应大小的钛网(60目)作为集流体,将两个电极膜包覆在钛网的两面,呈“三明治”结构,后置于辊压机中辊压,对辊间距为0.3mm,多次辊压后得到0.55~0.65mm厚的电极;
所述导电剂为乙炔炭黑、石墨烯、碳纳米管、黑磷、Ti4O7的一种。
7.根据权利要求6所述多元掺杂活性炭电极的制备方法,其特征在于,所述的电极膜的厚度为0.3~0.5mm。
8.根据权利要求1所述钴多元掺杂活性炭电极的制备方法,其特征在于,所述步骤⑸的集流体为不锈钢网或钛网;辊压制作而成的电极的厚度为0.5~0.8mm。
9.一种多元掺杂活性炭催化剂(CoOx@N-AC)的表征和氧还原电催化测试方法,其特征在于,包括以下步骤:
⑴称取设定量的活性炭粉末,通过比表面积测定仪测定介孔活性炭的氮气吸附曲线并计算活介孔性炭的比表面积,介孔活性炭的比表面积为1397.82m2/g,通过Barett-Joyner-Halenda(BJH)算法计算介孔活性炭的孔径分布,介孔活性碳的孔径分布为5~15nm;
⑵取设定量的CoOx@N-AC,通过X射线衍射仪测定CoOx@N-AC中的晶体结构,CoOx@N-AC中钴氧化物以CoO的晶体形态掺杂在介孔活性炭上;
⑶取设定量的CoOx@N-AC,通过X射线光电子能谱仪测定CoOx@N-AC中的元素组成和价态分布,CoOx@N-AC中的氮掺杂以石墨氮为主,Co元素中的2+的价态更多;
⑷取20mg CoOx@N-AC和2mg碳乙炔黑置于5ml无水乙醇中,加入10μl Nafion膜溶液,超声分散20min,后取10μl均匀涂覆于玻碳电极上,干燥后置于旋转圆环电极设备中,电解液的pH为3的0.5M Na2SO4溶液,在氧气饱和的条件下采用电化学工作站进行极化曲线的测定,扫描范围为0.2V(vs.Ag/AgCl)至-0.8V(vs.Ag/AgCl),电极转速为1600rpm;
⑸根据下述公式1和公式2分别计算电子转移数和双氧水得率,求得CoOx@N-AC的电子转移数和双氧水得率分别为2.4和67.35%,证明CoOx@N-AC具有极高的氧还原二电子传递选择性:
其中Id和Ir分别是盘电流和环电流(A),N是收集效率N=0.37。
10.根据权利要求9所述多元掺杂活性炭催化剂(CoOx@N-AC)的表征和氧还原电催化测试方法,其特征在于,所述步骤⑷进一步包括:以铂片(1cm*1cm)为阳极,以电极(1cm*1cm)为阴极,电解液为pH为3的0.5M Na2SO4电解液,在氧气饱和的条件下采用电化学工作站测定电极的Tafel曲线,扫描范围为开路电压±0.1V;以铂片(1cm*1cm)为阳极,以电极(1cm*1cm)为阴极,中间以阳离子交换膜相隔,电解液为pH为3的0.5M Na2SO4电解液,在氧气饱和的条件下以恒电流模式(10mA/cm2)电解1h,后采用草酸钛钾法测定电解液中双氧水的含量,并通过公式3计算得到电合成双氧水的电流效率,所述电极的双氧水产率为2.36±0.25,电合成双氧水的电流效率为63.25%;
其中n是电子转移数,V是电解液的体积(L),Q是电解过程的电量(C)。
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