CN111285446B - 一种Pd/NiCo2O4/Ni foam复合电极及其制备方法和应用 - Google Patents
一种Pd/NiCo2O4/Ni foam复合电极及其制备方法和应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 177
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 55
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 16
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- 238000001354 calcination Methods 0.000 claims abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
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- 238000009713 electroplating Methods 0.000 claims description 12
- 150000002940 palladium Chemical class 0.000 claims description 12
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- 238000004140 cleaning Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
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- 238000000151 deposition Methods 0.000 claims description 6
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
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- 239000004332 silver Substances 0.000 claims description 4
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- HXKWSTRRCHTUEC-UHFFFAOYSA-N 2,4-Dichlorophenoxyaceticacid Chemical group OC(=O)C(Cl)OC1=CC=C(Cl)C=C1 HXKWSTRRCHTUEC-UHFFFAOYSA-N 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003792 electrolyte Substances 0.000 description 5
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- 230000002378 acidificating effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- RFOHRSIAXQACDB-UHFFFAOYSA-M sodium;2-(2,4-dichlorophenoxy)acetate Chemical compound [Na+].[O-]C(=O)COC1=CC=C(Cl)C=C1Cl RFOHRSIAXQACDB-UHFFFAOYSA-M 0.000 description 2
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
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Abstract
本发明公开了一种Pd/NiCo2O4/Ni foam复合电极及其制备方法和应用,所示Pd/NiCo2O4/Ni foam复合电极是以泡沫镍为基体,先通过水热反应、煅烧两步处理过程,以在泡沫镍基体表面上形成NiCo2O4中间层,再电沉积钯纳米颗粒层而制得。本发明的复合电极采用绿色环保的方法合成,且对含氯有机污染物具有超高催化脱氯性能,并具备催化寿命长的特点,在电催化处理废水中的2,4‑D的应用中,具有非常广阔的应用前景。本发明的Pd/NiCo2O4/Ni foam复合电极,相比于同等脱氯效果的Pd/Ni foam电极,节省了大约75%的贵金属钯载量,从而大幅度地降低了含氯有机污染物脱氯处理的成本。
Description
技术领域
本发明涉及一种Pd/NiCo2O4/Ni foam复合电极及其制备方法和应用。
背景技术
含氯有机物作为广泛应用于农业、工业和医药业的原料,多制备用于除草、杀虫、灭菌、消毒和防腐,这些用途使得污染物直接排放到自然环境,造成污染。因此,自然环境中存在大量的农药残留,又由于自然演化作用,这些含氯有机物在土壤水体中渗流转化,最终进入到地下水系统,形成了地下水污染。含氯有机污染物具有高毒性、难降解性、持续稳定性、耐热性、生物富集、遗传毒害性等特点。值得一提的是,含氯有机污染物的毒性和持久性主要来自于氯元素。若能去除其中的氯元素,毒性会大大降低,去除氯后的芳香烃还可以通过生物过程完全降解。
贵金属钯催化剂在工业催化和环境治理中有着十分重要的作用。然而,在使用中存在众多局限性,比如钯属于贵金属元素,成本较高;化学沉积法负载纳米钯颗粒于泡沫镍基底上,由于其沉积的钯颗粒直径较大易发生团聚,阻碍其催化活性的发挥;使用后活性降低,限制其重复利用。
发明内容
针对现有技术存在的上述技术问题,本发明的目的在于提供一种Pd/NiCo2O4/Nifoam复合电极及其制备方法和应用。
所述的一种Pd/NiCo2O4/Ni foam复合电极,其特征在于所述复合电极是以泡沫镍为基体,先通过水热反应、煅烧两步处理过程,以在泡沫镍基体表面上形成NiCo2O4中间层,再电沉积钯纳米颗粒层而制得。
所述的一种Pd/NiCo2O4/Ni foam复合电极,其特征在于所述复合电极中,钯纳米颗粒在泡沫镍上的沉积量为0.25~0.3mg/cm2,优选为0.27mg/cm2;NiCo2O4中间层在泡沫镍上的负载量为0.2~0.3mg/ cm2。
所述的一种Pd/NiCo2O4/Ni foam复合电极的制备方法,其特征在于包括以下步骤:
1)泡沫镍预处理:将泡沫镍基体先用2-4mol/L的盐酸超声20-50min以去除其表面氧化层,再用无水乙醇清洗3-10min以去除其表面有机物,最后用蒸馏水反复清洗2~5次后,在空气中晾干,得到预处理过的泡沫镍基体;
2)NiCo2O4中间层的制备:将镍盐、钴盐、NH4F和CO(NH2)2溶于水中,配制得到反应液;将步骤1)所得预处理过的泡沫镍基体静置在反应液中,然后移入到反应釜中进行水热反应,反应结束后自然冷却至室温,将泡沫镍基体取出并依次用乙醇和去离子水清洗干净,晾干,然后在惰性气氛下煅烧,使泡沫镍基体上形成NiCo2O4中间层,得到NiCo2O4/Ni foam电极;
3)电沉积钯纳米颗粒层:电沉积过程在单室反应器中进行,单室反应器中盛有含有钯盐的酸性电镀液,以步骤2)所得的NiCo2O4/Ni foam电极作为阴极,铂电极为阳极,辅以银/氯化银电极作为参比电极;在含有钯盐的酸性电镀液中电沉积钯纳米颗粒层,电沉积方式为恒电位法,制得Pd/NiCo2O4/Ni foam复合电极。
所述的一种Pd/NiCo2O4/Ni foam复合电极的制备方法,其特征在于步骤2)中,水热反应的温度为110~130℃,优选为120℃;反应时间为3~7h,优选为5h。
所述的一种Pd/NiCo2O4/Ni foam复合电极的制备方法,其特征在于步骤2)中,所述惰性气氛的气体为Ar;煅烧过程为:从室温以2-3℃/min速率升温至300-400℃后,恒温煅烧1.5-3h,随后自然降温至室温。
所述的一种Pd/NiCo2O4/Ni foam复合电极的制备方法,其特征在于步骤3)中,所述酸性电镀液由钯盐和钠盐的混合水溶液组成,钯盐的浓度为0.5-2mol/L;所述钯盐为氯化钯,钠盐为氯化钠,钯盐和钠盐的摩尔比为1:20-40,优选为1:30。
所述的一种Pd/NiCo2O4/Ni foam复合电极的制备方法,其特征在于步骤3)采用恒电位法中,电位为-0.5V至-2V之间,优选-1V。
所述的Pd/NiCo2O4/Ni foam复合电极在电催化废水中的含氯有机污染物进行还原脱氯中的应用。
所述的Pd/NiCo2O4/Ni foam复合电极在电催化废水中的含氯有机污染物进行还原脱氯中的应用,其特征在于所述含氯有机污染物为2,4-二氯苯氧乙酸。
相对于现有技术,本发明取得的有益效果是:
1)本发明的Pd/NiCo2O4/Ni foam复合电极具有催化活性位点多、使用寿命长,贵金属钯使用量少、成本低等特点。利用Pd/NiCo2O4/Ni foam复合电极,通过电化学还原方法可实现水中含氯有机污染物的有效去除,操作简单,管理方便,具有广泛的社会和经济效益。本发明总体分两步制备Pd/NiCo2O4/Ni foam复合电极:第一步是利用先水热反应后煅烧的方法,制备出NiCo2O4中间层;第二步是利用电沉积的方法把钯颗粒负载到NiCo2O4表面。
2)本发明的复合电极采用绿色环保的方法合成,且对含氯有机污染物具有超高催化脱氯性能,并具备催化寿命长的特点,在电催化处理废水中的2,4-D的应用中,具有非常广阔的应用前景。本发明的Pd/NiCo2O4/Ni foam复合电极,相比于同等脱氯效果的Pd/Nifoam电极,节省了大约75%的贵金属钯载量,从而大幅度地降低了含氯有机污染物脱氯处理的成本。
附图说明
图1为本发明进行电催化还原脱氯装置的结构示意图;
图2为实施例1中步骤a所得Ni foam电极的电镜扫描图;
图3为实施例1中步骤b所得NiCo2O4/Ni foam电极的电镜扫描图;
图4为实施例1中步骤c所得Pd/NiCo2O4/Ni foam复合电极的电镜扫描图;
图5为实施例7所得Pd/NiCo2O4/Ni foam复合电极重复使用5次过程中,对含2,4-D废水的电催化还原脱氯结果图;
图1中:a-阳极池,b-阴极池,c-参比池,1-1阳极,1-2阴极,1-3阳离子交换膜,2-循环水浴池,3-电化学工作站。
具体实施方式
下面结合具体实施例对本发明作进一步说明,但本发明的保护范围并不限于此。
以下实施例1-7中,电催化还原脱氯装置的结构示意图如图1所示。
对照图1,所述电催化还原脱氯装置包括电解池、循环水浴池2和电化学工作站3。所述电解池包括存放阳极液及阳极1-1的阳极池a、存放阴极液及阴极1-2的阴极池b、存放饱和甘汞电极的参比池c(阴极池b与参比池c相连通)、阳离子交换膜1-3,所述阴极池b上部设置有取样口,所述阳极池a和阴极池b底部设有连通管道,所述连通管道设阳离子交换膜1-3将阳极池a和阴极池b分隔。其中,阳极1-1选用铂电极,阴极1-2选用Pd/NiCo2O4/Ni foam复合电极,阳极液为硫酸钠的水溶液,阴极液为硫酸钠与2,4-D的混合水溶液。阳极1-1、阴极1-2和饱和甘汞电极均与电化学工作站3相连接。
实施例1
制备一种Pd/NiCo2O4/Ni foam复合电极,包括以下步骤:
a、泡沫镍预处理:将厚度为1.2mm的、尺寸面积为4cm2(2cm × 2cm)的泡沫镍基体依次用3mol/L的盐酸超声30min以去除其表面氧化层,再用无水乙醇清洗5min以去除表面有机物,最后用蒸馏水反复清洗三次后,在空气中晾干,得到预处理过的泡沫镍基体。预处理过的泡沫镍基体的电镜扫描图如图2所示;
b、NiCo2O4中间层的制备:将Ni(NO3)2·6H2O、Co(NO3)2·6H2O、NH4F、CO(NH2)2以1:2:6:15的摩尔比溶于水中,其中Ni(NO3)2·6H2O在水中的浓度为0.00167mol/L,配制得到反应液A;将步骤a预处理过的泡沫镍基体静置在50mL配制的反应液A中,然后移入反应釜中进行水热反应,水热反应的温度为120℃,反应时间为5h。待反应结束后自然降温至室温,将反应后的泡沫镍基体取出,依次用乙醇和去离子水清洗干净,在空气中晾干,然后在管式炉中于通Ar的条件下进行煅烧,煅烧过程为:从室温以2℃/min速率升温至350℃后,恒温煅烧2h,随后自然降温至室温,即制得NiCo2O4/Ni foam电极。所得NiCo2O4/Ni foam复合电极的电镜扫描图如图3所示。可以观察到呈片状的NiCo2O4均匀的负载在泡沫镍基体上;
c、电沉积钯纳米颗粒层:电沉积过程在单室反应器中进行,以步骤b所得的NiCo2O4/Ni foam电极作为阴极,等面积的铂片(2cm × 2cm)为阳极,辅以银/氯化银电极作为参比电极。在20ml酸性电镀液中电沉积钯纳米颗粒层,电极间距为1cm,控制酸性电镀液温度为25℃,电沉积方式为恒电位法(电压为-1.0V),制得Pd/NiCo2O4/Ni foam复合电极。所得Pd/NiCo2O4/Ni foam复合电极的电镜扫描图如图4所示。可以观察到Pd颗粒分散在NiCo2O4表面。所得Pd/NiCo2O4/Ni foam复合电极中,Pd的负载量为0.27mg/cm2,且NiCo2O4中间层的负载量为0.25mg/ cm2。
所述酸性电镀液按如下组成配制:取氯化钯0.0887g和氯化钠0.8775g溶于500ml水中,配制得到所述的酸性电镀液。
上述实施例1制备的Pd/NiCo2O4/Ni foam复合电极,应用于含2,4-D废水的电催化还原脱氯反应,过程如下:
电催化还原脱氯装置为H型三室反应器,其结构示意图如图1所示,以实施例1制备的Pd/NiCo2O4/Ni foam复合电极为阴极,铂电极为阳极,阴极和阳极的电极面积均为4cm2(2cm × 2cm),辅以甘汞电极为参比电极,电极间距为7cm。恒电压为-1.5V,阴极池内的电解液为硫酸钠与2,4-D的混合水溶液(硫酸钠的浓度为2mmol/L,且2,4-D的浓度为0.045mol/L),以模拟天然有机废水,阴极池内电解液的反应体积为72ml。阳极池内的电解液为浓度为2mmol/L的硫酸钠水溶液,阳极池内电解液的反应体积为36ml。并且反应进行到不同的时刻对阴极池内电解液进行取样分析,进行电催化还原脱氯2h,结果如表1所示。
实施例2
本实施例2中,NiCo2O4/Ni foam复合电极的制备过程重复实施例1中a,b步骤。
实施例2制备的NiCo2O4/Ni foam复合电极,应用于含2,4-D废水的电催化还原脱氯反应,电催化还原脱氯反应的实验过程与实施例1相同,进行电催化还原脱氯2h的结果如表1所示。
实施例3
本实施例3中,Pd/NiCo2O4/Ni foam复合电极的制备过程重复实施例1。
实施例3制备的Pd/NiCo2O4/Ni foam复合电极,应用于含2,4-D废水的电催化还原脱氯反应,电催化还原脱氯反应的实验过程与实施例1相同,不同之处在于将恒电压替换成-1.2V,其余电催化还原脱氯反应的实验步骤均与实施例1相同,进行电催化还原脱氯2h的结果如表1所示。
实施例4
本实施例4中,Pd/NiCo2O4/Ni foam复合电极的制备过程重复实施例1。
实施例4制备的Pd/NiCo2O4/Ni foam复合电极,应用于含2,4-D废水的电催化还原脱氯反应,电催化还原脱氯反应的实验过程与实施例1相同,不同之处在于将恒电压替换成-2.0V,其余电催化还原脱氯反应的实验步骤均与实施例1相同,进行电催化还原脱氯2h的结果如表1所示。
实施例5
制备一种Pd/Ni foam电极,包括以下步骤:
1)泡沫镍预处理:将厚度为1.2mm的、尺寸面积为4cm2(2cm × 2cm)的泡沫镍基体依次用3mol/L的盐酸超声30min以去除其表面氧化层,再用无水乙醇清洗5min以去除表面有机物,最后用蒸馏水反复清洗三次后,在空气中晾干,得到预处理过的泡沫镍基体;
2)电沉积钯纳米颗粒层:电沉积过程在单室反应器中进行,以步骤1)所得的泡沫镍基体作为阴极,等面积的铂片(2cm × 2cm)为阳极,辅以银/氯化银电极作为参比电极。在20ml酸性电镀液中电沉积钯纳米颗粒层,电极间距为1cm,控制酸性电镀液温度为25℃,电沉积方式为恒电位法(电压为-1.0V),制得Pd/Ni foam电极。所得Pd/Ni foam电极中,Pd的负载量为0.27mg/cm2。
所述酸性电镀液按如下组成配制:取氯化钯0.0887g和氯化钠0.8775g溶于500ml水中,配制得到所述的酸性电镀液。
实施例5制备的Pd/Ni foam电极,应用于含2,4-D废水的电催化还原脱氯反应,电催化还原脱氯反应的实验过程与实施例1相同,进行电催化还原脱氯2h的结果如表1所示。
实施例6
本实施例6中,Pd/Ni foam电极的制备过程重复实施例5,不同之处在于:“将步骤2)中酸性电镀液的体积量替换为80mL”,最终制得的Pd/Ni foam电极中,Pd的负载量为1.06mg/cm2。
实施例6制备的Pd/Ni foam电极,应用于含2,4-D废水的电催化还原脱氯反应,电催化还原脱氯反应的实验过程与实施例1相同,进行电催化还原脱氯2h的结果如表1所示。
利用实施例1~6所得的电极对2,4-D进行电催化还原脱氯2h,试验结果如表1所示。
表1. Pd/NiCo2O4/Ni foam复合电极和Pd/Ni foam电极在不同电位下对2,4-D进行电催化还原脱氯2h的去除率
从表1可以看出,制得的Pd/NiCo2O4/Ni foam复合电极在保持较好的脱氯性能的同时还降低了贵金属钯的使用量。这可能是因为,在泡沫镍基体表面引入NiCo2O4中间层能够调控电极表面的电子分布,NiCo2O4/Ni foam复合电极表面加入少量的Pd后,即可有较好的催化反应效果,从而起到降低Pd载量和节约成本的作用。
本发明以2,4-二氯苯氧乙酸(2,4-D)为代表性污染物,进行电化学还原处理去除废水中难降解有机污染物。如表1所示,泡沫镍负载的NiCo2O4本身不显示脱氯活性,但泡沫镍负载的Pd/NiCo2O4显示了远超泡沫镍负载的Pd电极的脱氯活性。只有当加大Pd的载量至原来的4倍时,泡沫镍负载的Pd电极才能达到与泡沫镍负载的Pd/NiCo2O4相似的脱氯性能。由此可见,NiCo2O4的加入调控了电极的电子分布,极大地改善了其脱氯性能,相当于节省了大约75%的贵金属Pd。
实施例7
本实施例中,Pd/NiCo2O4/Ni foam复合电极的制备过程重复实施例1。
实施例7制备的Pd/NiCo2O4/Ni foam复合电极,应用于含2,4-D废水的电催化还原脱氯反应,电催化还原脱氯反应的实验过程与实施例1相同,电催化还原脱氯反应过程中多次对废水进行取样分析,电解2h后结束本次反应,并更换新鲜废水进行下一次重复电催化反应。由此Pd/NiCo2O4/Ni foam复合电极重复使用5次过程中,对含2,4-D废水的电催化还原脱氯结果如图5所示。
从图5可以看出,在Pd/NiCo2O4/Ni foam复合电极重复使用5次的过程中,其电催化性能稳定性较好。
本说明书所述的内容仅仅是对发明构思实现形式的列举,本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式。
Claims (7)
1.一种Pd/NiCo2O4/Ni foam复合电极,其特征在于所述复合电极是以泡沫镍为基体,先通过水热反应、煅烧两步处理过程,以在泡沫镍基体表面上形成NiCo2O4中间层,再电沉积钯纳米颗粒层而制得;
所述的Pd/NiCo2O4/Ni foam复合电极的制备方法,包括以下步骤:
1)泡沫镍预处理:将泡沫镍基体先用2-4mol/L的盐酸超声20-50min以去除其表面氧化层,再用无水乙醇清洗3-10min以去除其表面有机物,最后用蒸馏水反复清洗2~5次后,在空气中晾干,得到预处理过的泡沫镍基体;
2)NiCo2O4中间层的制备:将镍盐、钴盐、NH4F和CO(NH2)2溶于水中,配制得到反应液;将步骤1)所得预处理过的泡沫镍基体静置在反应液中,然后移入到反应釜中进行水热反应,反应结束后自然冷却至室温,将泡沫镍基体取出并依次用乙醇和去离子水清洗干净,晾干,然后在惰性气氛下煅烧,使泡沫镍基体上形成NiCo2O4中间层,得到NiCo2O4/Ni foam电极;
3)电沉积钯纳米颗粒层:电沉积过程在单室反应器中进行,单室反应器中盛有含有钯盐的酸性电镀液,以步骤2)所得的NiCo2O4/Ni foam电极作为阴极,铂电极为阳极,辅以银/氯化银电极作为参比电极;在含有钯盐的酸性电镀液中电沉积钯纳米颗粒层,电沉积方式为恒电位法,制得Pd/NiCo2O4/Ni foam复合电极;
所述酸性电镀液由钯盐和钠盐的混合水溶液组成,钯盐的浓度为0.5-2mol/L;所述钯盐为氯化钯,钠盐为氯化钠,钯盐和钠盐的摩尔比为1:20-40。
2.如权利要求1所述的一种Pd/NiCo2O4/Ni foam复合电极,其特征在于所述复合电极中,钯纳米颗粒在泡沫镍上的沉积量为0.25~0.3mg/cm2;NiCo2O4中间层在泡沫镍上的负载量为0.2~0.3mg/cm2。
3.如权利要求1所述的一种Pd/NiCo2O4/Ni foam复合电极,其特征在于步骤2)中,水热反应的温度为110~130℃;反应时间为3~7h。
4.如权利要求1所述的一种Pd/NiCo2O4/Ni foam复合电极,其特征在于步骤2)中,所述惰性气氛的气体为Ar;煅烧过程为:从室温以2-3℃/min速率升温至300-400℃后,恒温煅烧1.5-3h,随后自然降温至室温。
5.如权利要求1所述的一种Pd/NiCo2O4/Ni foam复合电极,其特征在于步骤3)采用恒电位法中,电位为-0.5V至-2V之间。
6.如权利要求1所述的Pd/NiCo2O4/Ni foam复合电极在电催化废水中的含氯有机污染物进行还原脱氯中的应用。
7.如权利要求6所述的应用,其特征在于所述含氯有机污染物为2,4-二氯苯氧乙酸。
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