CN107364934A - 电催化还原复合电极、制备方法及其应用 - Google Patents
电催化还原复合电极、制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种电催化还原复合电极、制备方法及其应用,所述电极以石墨毡为基底,其基底上依次沉积多壁碳纳米管、镍金属层和钯金属层;其步骤为:首先制备多壁碳纳米管/石墨毡电极;后将该电极置于镍盐溶液中浸泡,通过高温氮气还原在其表面形成镍金属层;再在钯盐溶液中,通过直接金属还原形成钯金属层,制备出镍钯双金属层复合电极。本发明制备的复合电极催化活性高、稳定性好,能够快速高效电催化处理水中硝基苯类、氯酚类物质。
Description
技术领域
本发明涉及一种用于水中硝基苯和氯酚类污染物电化学还原脱硝和脱氯的复合电极,属于电化学水处理技术领域。
背景技术
硝基苯类和氯酚类污染物存在于工业废水中,是非常典型的持久性有机污染物,广泛存在于化工、染料、农药和制药等工业部门排放的废水中,具有排放量大、难生物降解、有毒性或“三致”(致癌、致畸、致突变)作用等特点。这两类物质均在苯环上含有强吸电子基团,如硝基和氯基。由于硝基苯类和氯酚类污染物的毒性和稳定性,其在环境中的残留和积累,以及如何减轻或者消除这类化合物对环境的污染及毒性,引起了人们的日益关注。
目前,硝基苯类和氯酚类污染物的去除方法有处理方法主要有生物法、吸附法、高级氧化法和金属还原法。吸附法富集分离后的污染物处理不当会导致二次污染。生物处理方面,由于硝基和氯基的存在使好氧生物氧化酶对苯环的亲电子攻击受到阻滞,因而对于这两类污染物的处理效率很低。Fenton氧化、光催化氧化和超声空化等高级氧化技术发展迅速,但依然存在处理效率低、成本高等缺陷,离推广使用仍有较大差距。金属还原法处理受pH值、金属粒径与比表面积、混合搅拌速度等多个因素影响,存在金属易钝化、传质效率低、生成高毒终产物等缺陷。
电化学还原法直接通过电极进行界面反应,通过控制电流实现物质的还原,是一种高效、无副产物、无二次污染的环境友好技术,在废水中生物难降解有机物的去除的环境污染治理方面,越来越受到人们的重视。电化学脱氯和脱硝得到了大量的研究,但因其在处理硝基苯类和氯酚类污染物时电流效率低、电极制备成本较高、催化活性一般等原因并没有得到广泛的推广,高效稳定的电极仍然是电化学研究中的重点。在传统电化学水处理中使用的多为板材电极,但是在其平板结构上,污染物的传质方向和电流方向垂直,不利用电子的利用,而且电极上面会形成一层浓差极化薄膜,这会阻碍反应物质的传质,不利用反应的发生。而三维的结构的电极具有更大的反应面积和更好的电流传质作用,并且多孔的结构有利用反应物质的传递,所以三维结构的电极具有很好的应用前景。石墨毡(GF)是一种典型的廉价多孔,高比表面积,耐高温耐腐蚀的三维无机碳材料,适合用于电化学水处理领域,但是其相比于金属具有导电性较差、疏水等缺点。
发明内容
本发明的目的是提供一种具有高效电化学还原能力的镍钯双金属层复合电极(Pd-Ni/MWCNTs/GF电极)及其制备方法,并将其用在对水中硝基苯和氯酚类污染物的电化学还原脱硝和脱氯上。
实现本发明目的的技术解决方案是:
本发明所述的复合电极,以石墨毡为基底,其基底上依次沉积多壁碳纳米管、镍金属层和钯金属层。
上述复合电极的制备方法,包括以下步骤:
(1)取经预处理的石墨毡作为阴极,钛板作为阳极,置于多壁碳纳米管悬浮液中,以5-30mA电流进行电沉积,得到多壁碳纳米管/石墨毡电极;
(2)取步骤(1)所得电极,置入镍盐溶液中,浸泡;
(3)取步骤(2)所得材料,在通入氮气的管式炉中,加热至750±20℃,持续烧结3小时,得到镍/多壁碳纳米管/石墨毡电极;
(4)取步骤(4)所得电极,浸入钯盐溶液中,放入摇床至溶液无色后取出,洗净后、干燥,得到所述的复合电极。
本发明制备的复合电极在电催化硝基苯脱硝反应中的应用。
本发明制备的复合电极在电催化对氯酚脱氯反应中的应用。
与现有技术相比,本发明的优点是:
(1)本发明采用三维结构的石墨毡(GF)作为基底,其具有廉价多孔,高比表面积,耐高温耐腐蚀的优点,且使用浓酸对GF进行粗化,提升了它的亲水性,并使其表面粗糙易于负载物质。
(2)本发明利用电化学沉积多壁碳纳米管(MWCNTs)作为中间层,增大了石墨毡的比表面积,增强其导电性,并且可以固定负载金属。
(3)通过高温氮气还原在其表面形成镍金属层;然后在钯盐溶液中,通过直接金属还原形成钯金属层,制备出镍钯双金属层复合电极,由于双金属层的存在,其具有高的反应活性和稳定性。
(4)本发明制备出的电极,用于电化学还原硝基苯脱硝,脱硝效率高、产物成分单一,避免了其他化学方法产生成分复杂的二次污染物。
(5)本发明制备出的电极,用于电化学还原氯酚脱氯,脱氯效率高、产物成分单一,避免了其他化学方法产生成分复杂的二次污染物。
(6)本发明所制备的双金属层电极与单金属层的Pd /MWCNTs/GF电极相比,该电极能够快速、高效地去除硝基苯和对氯酚。
(7)本发明所制备的电极催化活性高、稳定性好,电催化处理水中硝基苯类和氯酚类物质快速高效,具有应用前景。
附图说明
图1为实施例1中所述的MWCNTs/GF(a)、Ni/MWCNTs/GF(b)、Pd-Ni/MWCNTs/GF(c)电极的表面形貌图。
图2为实施例1中所制备复合电极的X射线衍射分析图谱。
图3为实施例1和对比例1中硝基苯的还原效率-时间曲线。
图4为实施例1和对比例1中对氯酚的还原效率-时间曲线。
图5为实施例1和对比例1中电极反复使用10次反应速率的变化图。
具体实施方式
下面结合实施例对本发明进行详细描述。
本发明采用浓酸将GF进行腐蚀粗化处理,增强其亲水性,并使其表面结构粗糙易于后续制备,然后通过电沉积法将多壁碳纳米管(MWCNTs)沉积在石墨毡上,增大其比表面积,增强其导电性,并且可以固定负载金属。后将石墨毡置于镍盐溶液中浸泡,通过高温氮气还原在其表面形成镍金属层;然后在钯盐溶液中,通过直接金属还原形成钯金属层,制备出镍钯双金属层复合电极,用于水中硝基苯类和氯酚类的电化学脱硝和脱氯。其双金属层即可以提高反应的活性,又可以提高电极的稳定性。本发明以电化学脱硝和脱氯为目标,制备出一个比表面积大、具有高催化还原活性的双金属层复合电极,可以改进现有电极存在的催化活性低、催化剂不稳定等缺点,具有创造性。
在下述实验中,本发明制得的Pd-Ni/MWCNTs/GF电极和现有的GF电极、和对比例1中的Pd/MWCNTs/GF电极分别作为电催化反应器所用的阴极;所用的阳极为钛基形稳电极,涂层钌铱氧化物,中间用阳离子交换膜隔开。硝基苯或对氯酚和硫酸钠作为电解质通入电催化反应器,采用恒电流法,电流密度值为1-10mA/cm2,对硝基苯或对氯酚进行电还原脱硝。反应过程中充分搅拌阴极室,反应时间为30min。
本发明所述的复合电极的制备方法,包括以下步骤:
(1)石墨毡(GF)预处理:石墨毡用丙酮,甲醇各超声二十分钟洗去表面有机物,后用蒸馏水洗净;然后浸入1:1体积比的浓硝酸和浓硫酸混合溶液中1h,进行腐蚀粗化处理;
(2)多壁碳纳米管(MWCNTs)悬浮液的配制:将0.1-0.5gMWCNTs加入一定浓度的十六烷基三甲基溴化铵溶液中进行充分超声,制得反应溶液;
(3)MWCNTs/GF电极的制备:取步骤(1)经预处理的GF作为阴极,钛板作为阳极,置入步骤(2)所得的反应溶液中,以5-30mA电流进行30min电沉积,得到MWCNTs/GF电极;
(4)镍盐溶液的配制:将50-200mmol/L硝酸镍和尿素溶入去离子水中,反复搅拌得到镍盐溶液;
(5)取步骤(3)所得的MWCNTs/GF,置入步骤(4)所得的镍盐溶液中,浸泡12h;
(6)取步骤(5)所得的材料,在通入氮气的管式炉中,加热至750℃,持续3小时,得到Ni/MWCNTs/GF电极;
(7)钯盐溶液的配制:将1-20mmol/L氯化钯和氯化钠溶于100mL水中,超声得到钯盐溶液;
(8)取步骤(6)所得的材料,浸泡入(7)所得的钯盐溶液中,放入摇床至溶液无色后取出,用去离子水洗净后放入烘箱80℃烘干,得到所述的镍钯双金属层复合电极(Pd-Ni/MWCNTs/GF电极)。
实施例 1(Pd-Ni/MWCNTs/GF电极)
(1)石墨毡(GF)预处理:GF用丙酮,甲醇各超声二十分钟洗去表面有机物,后用蒸馏水洗净。然后浸入1:1体积比的浓硝酸和浓硫酸混合溶液中1h,进行腐蚀粗化处理;
(2)多壁碳纳米管(MWCNTs)悬浮液的配置:将0.1-0.5gMWCNTs加入一定浓度的十六烷基三甲基溴化铵溶液中进行充分超声制得反应溶液;
(3)MWCNTs/GF电极的制备:取步骤(1)处理干净的GF作为阴极,钛板电极作为阳极,置入步骤(2)所得的MWCNTs悬浮液中,以5-30mA电流进行30min电沉积,得到MWCNTs/GF电极(电镜扫描照片见图1)。
(4)镍盐溶液的配置:将50-200mmol/L硝酸镍和尿素溶入去离子水中,反复搅拌得到镍盐溶液。
(5)取步骤(3)所得的MWCNTs/GF,置入步骤(4)所得的镍盐溶液中,浸泡12h。
(6)取步骤(5)所得的材料,在通入氮气的管式炉中,加热至750℃,持续3小时,得到Ni/MWCNTs/GF电极(电镜扫描照片见图1)。
(7)钯盐溶液的配置:将1-20mmol/L氯化钯和氯化钠溶于100mL水中,超声得到钯盐溶液。
(8)取步骤(6)所得的材料,浸泡入(7)所得的钯盐溶液中,放入摇床至溶液无色后取出,用去离子水洗净后放入烘箱80℃烘干,制备出 Pd-Ni/MWCNTs/GF电极(电镜扫描照片见图1)。双金属均很好的负载于电极表面(X射线衍射图谱见图2)。
(9)硝基苯的电化学还原:还原反应在双室电解池中进行,阴阳两室之间用阳离子交换膜隔开。阳极使用钌铱钛电极,阴极步骤8制备的Pd-Ni/MWCNTs/GF电极,电解液采用50mmol/L的硫酸钠和100 mg/L的硝基苯混合溶液,将电解液置于电催化反应器中进行恒电流反应,其电流密度为10 mA/cm2,在二十分钟内对于硝基苯的去除效率达到100%,见图3。
(10)对氯酚的电化学还原:还原反应在双室电解池中进行,阴阳两室之间用阳离子交换膜隔开。阳极使用钌铱钛电极,阴极步骤8制备的Pd-Ni/MWCNTs/GF电极,电解液采用50 mmol/L的硫酸钠和100 mg/L的对氯酚混合溶液,将电解液置于电催化反应器中进行恒电流反应,其电流密度为10 mA/cm2,在三十分钟内对于对氯酚的脱氯效率达到100%,见图4。
(11)电极稳定性测试:反应条件如步骤10,反应11次,对氯酚的反应速率为0.161min-1,没有明显下降,见图5。
对比例1(Pd/MWCNTs/GF电极)
(1)石墨毡(GF)预处理:同实例1;
(2)多壁碳纳米管(MWCNTs)悬浮液的配置:同实例1;
(3)MWCNTs/GF电极的制备:同实例1;
(4)钯盐溶液的配置:同实例1;
(5)取步骤(3)所得的MWCNTs/GF为阴极,铂片为阳极,采用恒电流法在步骤4所配制的钯盐溶液中进行电沉积,电流密度为5 mA/cm2,沉积时间为1h,制出Pd/MWCNTs/GF电极(对比电极1)
(6)硝基苯的电化学还原:以对比电极1为工作电极,还原条件与实施例的步骤9相同,在三十分钟内对于硝基苯的去除效率达到91%,见图3。
(7)对氯酚的电化学还原:以对比电极1为工作电极,脱氯条件与实施例的步骤10相同,在三十分钟内对于对氯酚的脱氯效率达到96%,见图4。
(8)电极稳定性测试:反应条件与实施例的步骤10相同,反应11次,对氯酚的反应速率为0.009 min-1,有了大幅度的下降,见图5。
实施例和对比例的结果比较表明,镍钯双金属层复合电极相比于单金属层电极,增强了载钯电极的催化活性,还原试验结果表明,能够实现硝基苯和对氯酚的快速高效还原,并且双金属电极稳定性相比于单金属电极有了很大的提升,具有更好的处理含有这几类物质废水的前景。
Claims (10)
1.电催化还原复合电极,以石墨毡为基底,其特征在于,其基底上依次沉积多壁碳纳米管、镍金属层和钯金属层。
2.如权利要求1所述的复合电极,其特征在于,由以下步骤制备:
(1)取经预处理的石墨毡作为阴极,钛板作为阳极,置于多壁碳纳米管悬浮液中,以5-30mA电流进行电沉积,得到多壁碳纳米管/石墨毡电极;
(2)取步骤(1)所得电极,置入镍盐溶液中,浸泡;
(3)取步骤(2)所得材料,在通入氮气的管式炉中,加热至750±20℃,持续烧结3小时,得到镍/多壁碳纳米管/石墨毡电极;
(4)取步骤(4)所得电极,浸入钯盐溶液中,放入摇床至溶液无色后取出,洗净后、干燥,得到所述的复合电极。
3.如权利要求2所述的复合电极,其特征在于,步骤(1)中,经预处理的石墨毡是采用丙酮,甲醇各超声二十分钟洗去表面有机物,后用蒸馏水洗净,然后浸入1:1体积比的浓硝酸和浓硫酸混合溶液中1h,进行腐蚀粗化处理后得到。
4.如权利要求2所述的复合电极,其特征在于,步骤(1)中,多壁碳纳米管悬浮液的溶剂为十六烷基三甲基溴化铵溶液,多壁碳纳米管悬浮液的浓度为0.3g/L。
5.如权利要求2所述的复合电极,其特征在于,步骤(1)中,以5-30mA电流电沉积30min。
6.如权利要求2所述的复合电极,其特征在于,步骤(2)中,镍盐溶液通过将硝酸镍和尿素溶入去离子水中制得,镍盐溶液中硝酸镍浓度为100mmol/L,尿素为150mmol/L;浸泡时间为12h。
7.如权利要求2所述的复合电极,其特征在于,步骤(4)中,钯盐溶液通过将氯化钯和氯化钠溶于水中超声后得到,钯盐溶液中的氯化钯浓度为10mmol/L,氯化钠的浓度为10mmol/L;干燥温度不高于80℃。
8.如权利要求1-7任一所述的电催化还原复合电极的制备方法。
9.如权利要求1-7任一所述的电催化还原复合电极在电催化硝基苯脱硝反应中的应用。
10.如权利要求1-7任一所述的电催化还原复合电极在电催化对氯酚脱氯反应中的应用。
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