CN113699547A - 一种多孔合金电极的制备方法及应用 - Google Patents
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Abstract
本发明公开了一种多孔合金电极的制备方法,该多孔合金电极是采用脱合金化法制得Ni‑Cu‑La‑P多孔合金电极,采用滴涂法将纳米γ‑Fe2O3负载到多孔合金电极上,再通过电沉积法在电极表面负载光催化剂制得,将所制得多孔合金电极应用在光照条件下处理含微塑料的有机废水且降低析氢过电位中,不仅可明显降低电解水阴极析氢过电位,还能去除水中微塑料、有机污染物,且去除率为90%以上,本发明制备工艺简单,易操作,电极使用方便,适于工业化生产和市场推广应用。
Description
技术领域
本发明属于电解水制氢技术领域,具体涉及一种多孔合金电极的制备方法及其在在光照条件下处理含微塑料的有机废水且降低析氢过电位中的应用。
背景技术
热力学上水电解的理论电压为1.23V,但是现实情况下由于阴极析氢过电位过大等因素,导致实际电解水电压大于理论电压,为实现大规模电解水制氢的关键就是降低电解能耗、减小析氢过电位。
为减小析氢过电位,通常通过筛选优良电极材料和增大电极表面积两种方式。贵金属Pt被广泛应用于析氢材料,但贵金属含量少,成本高。对于筛选性能优良的电极材料通常是筛选出价格便宜、析氢过电位小的材料。过渡金属Ni、Fe等金属及其金属合金具有优良的导电性能,同时具有较小的析氢过电位,常用的有镍系合金、铁系合金。同时有研究发现,在合金中添加一些稀土金属能有效改善电极材料的结构和电流分布状况,能够很好的降低析氢过电位。对于增大电极表面积,可通过不同的制备方法制备多孔电极,常用的制备电极的方法有电沉积法、模板法、脱合金化法等,其中脱合金化法因制备过程简单且易制备多孔电极而应用广泛。
纤维微塑料在大量的研究中都被证明是水环境中的主要微塑料污染物,这些纤维微塑料除了来自丢弃在水环境中的鱼线、渔网的破损和降解(次生微塑料)之外,更多来自合成纤维织物在洗护过程中细小纤维的脱落(初生微塑料),然而,纤维微塑料在各种环境下更易发生破碎,导致大量次生微塑料的释放,使微塑料污染进一步加剧。
微塑料污染严重威胁全球生态安全,但是现有技术无法有效应对微塑料危机,急需一种高效低能耗技术对其进行降解。分布广泛的微塑料广泛分布在水体中,在电解水析氢过程中参与反应,使其产生大量的副反应影响析氢效率,增加析氢能耗。为保证氢气质量、减少析氢过程中产生的过多的能耗,减少析氢过电位的同时保证水源质量成为研究重点。
发明内容
针对现有技术的不足,本发明提供了一种多孔合金电极的制备方法,本发明方法采用脱合金化法制备Ni-Cu-La-P多孔合金电极,采用滴涂法将纳米γ-Fe2O3负载到多孔合金电极上,再通过电沉积法在电极表面负载光催化剂,使电极材料不仅能极大减小析氢过电位,提高产氢能力,还能在电催化刺激下使光催化剂具有高强活性,从而降解电解液中难降解的有机物,脱合金化法旨在制备出具有高空隙度的电极材料,选择Ni、Cu金属参杂稀土金属La作为电极主体,Ni过渡金属及Cu具有中等的吸附、脱附氢气的能力和较低的析氢过电位,通过P粉对电极中电流进行调节,改善电流活性位点分布,加入稀土金属La可进一步调节电极电流流向,电子密度,进一步降低析氢过电位。通过电沉积法将光催化剂负载在电极表面,通过控制循环圈数可以调整光催化剂在电极表面地厚度,其中纳米γ-Fe2O3催化剂在电流作用下失去电子易形成Fe2+,协同光催化产生的•OH、•O2等自由基激活芬顿反应,极大增强电极的降解能力,同时,选择光催化剂在光照条件下能激发电子转移,成为激发态,便可有效调整电子在电极表面地转移,且具有一定的光催化氧化还原能力,能去除水中微塑料、有机污染物。
本发明方法具体操作如下
(1)将质量百分比50%-80%Al粉、7.5%-25%Ni粉、5%-15% Cu粉、2%-4%P粉、0.5%-1%La粉加入真空球磨罐内,在N2气氛下球磨混料100-120min;
所述Ni粉的粒径<20μm,Al粉的粒径<20μm,La粉的粒径<10μm,Cu粉的粒径<20μm,P粉粒径<10μm;
真空球磨罐中球料质量比为4-6:1,转数为80-200r/min,每运行15-45min,间隙10-15min;
(2)将混合物料放入模具中,在10-20MPa下压制成型得到粗胚,将粗胚置于刚玉坩埚中,然后置于真空高频感应熔炼炉中熔炼,在Ar气氛、850-900℃下保温2-8h,将熔炼后的合金取出冷却后,切割分成小块,打磨表面氧化层备用;
(3)将切割后的合金小块放入真空甩带机中,制得宽度为2-5mm,厚度为20-50μm的Ni-Cu-La-P-Al合金条带;
(4)将合金条带置于质量浓度20%-45%的NaOH溶液中,在40-80℃下进行脱Al处理12-48h,获得多孔Ni-Cu-La-P合金条带,合金条带用去离子水和乙醇洗涤至中性,干燥后;
(5)先采用滴涂法将纳米γ-Fe2O3负载到多孔合金电极上,再采用电沉积法在多孔合金电极上表面沉积BiOX、MnO2、ZnO、SnO2、ZrO2、CdS中的一种,其中X为卤素,制得多孔合金电极。
本发明另一目的是将上述方法制得的多孔合金电极应用在在光照条件下处理含微塑料的有机废水且降低析氢过电位中。
本发明的优点和技术效果:
1、本发明电极材料使用脱合金化法制备,具有高表面积,能提供更多的反应位点,使用Ni-Cu-La-P合金作为主体,过渡金属Ni具有较低的析氢过电位,P通过调节电流分布,使活性位点分布均匀,使电解水产氢需要更低的电压;
2、本发明使用稀土金属La的加入有利于调节材料结构,减少电极腐蚀,提高电极稳定性,同时增大电流密度,减小析氢过电位;
3、本发明在Ni-Cu-La-P多孔电极表面负载纳米γ-Fe2O3后再采用电沉积法在多孔合金电极上表面负载光催化剂修饰电极,可降低氢脆现象,增加电极强度,减少电极腐蚀,延长电极使用寿命;γ-Fe2O3能在阴极间接激发芬顿反应,与光催化剂配合后,通过光照能激发光催化剂光催化活性,能促进电子转移,降解水中微塑料、有机污染物。
4、本发明制备工艺简单,易操作,电极使用方便,适于工业化生产和市场推广应用。
具体实施方式
下面通过具体实施案例对本发明进行进一步详细描述,但本发明保护范围不仅限于以下实施例。
实施例1:本实施例多孔合金电极的制备方法如下:
(1)将质量百分比75%Al粉、12.5%Ni粉、10% Cu粉、2%P粉、0.5%La粉的比例将上述粉末加入真空球磨罐内,通入N2,将球磨罐放进球磨机中,球料质量比为5:1,转数为100r/min,每运行30min,间隙10min,总时长120min;
(2)采用等静压机进行压制,将混合物料放入直径15mm模具中,在20MPa下压制20min成型得到直径15mm的粗胚,将粗胚置于刚玉坩埚中,然后置于真空高频感应熔炼炉中熔炼,在Ar气氛、900℃下保温3h,将熔炼后的合金取出冷却后,线切割成1cm3的小正方体块状,打磨表面氧化层;
(3)将小方块放入石英管中并置于真空甩带机中,加热熔化金属,在石英管上方通入0.12-0.15MPa氩气,使呈液态的合金由石英管末端喷出至25r/s的铜辊上,合金溶液与铜辊接触并被甩出发生快速凝固,形成Ni-Cu-La-P-Al合金条带;
(4)将合金条带置于质量浓度25%的NaOH溶液中,在65℃下进行脱Al处理32h,获得多孔Ni-Cu-La-P合金条带,合金条带用去离子水和乙醇洗涤至中性,60℃干燥6h后;
(5)先采用滴涂法将纳米γ-Fe2O3负载到多孔合金电极上,具体是将Fe(NO3)3∙9H2O溶于乙二醇制成2mmol/L的Fe(NO3)3溶液,然后将Fe(NO3)3溶液均匀滴涂到多孔Ni-Cu-La-P合金条带表面,然后在80℃真空干燥箱中烘干,重复上述涂滴过程5次后,在马弗炉中以1℃/min升温速度升温至500℃处理3 h,得到负载纳米γ-Fe2O3的多孔Ni-Cu-La-P电极;
(6)使用三电极体系,将制得的负载纳米γ-Fe2O3的多孔Ni-Cu-La-P薄片作为工作电极,铂电极为辅助电极,饱和甘汞电极为参比电极,电解质溶液为8mmol/LMnSO4+0.1mol/LH2SO4溶液,采用循环伏安法在多孔Ni-Cu-La-P合金电极上电沉积MnO2颗粒,扫描范围为-1-1.6V,扫描速率10mV/s,扫描圈数为40圈;用去离子水除去电极表面多余的杂质,在80℃干燥4h,然后再300℃下烧结3h,制得γ-Fe2O3/MnO2修饰得多孔Ni-Cu-La-P合金电极;
所制的多孔电极片宽2-5mm,厚30μm,比表面积126m3/g,孔径尺寸为100-300nm;在室温下,将制备γ-Fe2O3/MnO2修饰得多孔Ni-Cu-La-P合金电极作为工作电极进行电化学测试,结果表明,在电流密度为150mA/cm3时,析氢起始电位为-1.44V,析氢过电位为70mV;将本实施例电极用于含微塑料的甲基橙废水的处理,其中微塑料PVC含量为0.5mg/L,粒径小于5mm,有机物的初始含量1mg/L,将制备的多孔电极作为阴极,不锈钢电极做阳极,施加1.3V电压,在此电压作用下阴极开始产氢,同时在电极上方施加345nm荧光灯,产生紫外辐射,在此条件下处理10h后,经检测有机废水中甲基橙浓度为0.04mg/L,降解率达到96%,PVC含量仅0.04mg/L,降解率达到92%,且电极工作10h后,性能依旧稳定,说明电极材料具有较强的稳定性。
实施例2:本实施例多孔合金电极的制备方法如下:
(1)将质量百分比55%Al粉、25%Ni粉、15% Cu粉、4%P粉、1%La粉的比例将上述粉末加入真空球磨罐内,通入N2,将球磨罐放进球磨机中,球料质量比为4:1,转数为150r/min,每运行20min,间隙15min,总时长110min;
(2)采用等静压机进行压制,将混合物料放入直径15mm模具中,在15MPa下压制30min成型得到直径15mm的粗胚,将粗胚置于刚玉坩埚中,然后置于真空高频感应熔炼炉中熔炼,在Ar气氛、900℃下保温4h,将熔炼后的合金取出冷却后,线切割成1cm3的小正方体块状,打磨表面氧化层;
(3)将小方块放入石英管中并置于真空甩带机中,加热熔化金属,在石英管上方通入0.12-0.15MPa氩气,使呈液态的合金由石英管末端喷出至25r/s的铜辊上,合金溶液与铜辊接触并被甩出发生快速凝固,形成Ni-Cu-La-P-Al合金条带;
(4)将合金条带置于质量浓度35%的NaOH溶液中,在45℃下进行脱Al处理40h,获得多孔Ni-Cu-La-P合金条带,合金条带用去离子水和乙醇洗涤至中性,65℃干燥5h后;
(5)先采用滴涂法将纳米γ-Fe2O3负载到多孔合金电极上,具体是将Fe(NO3)3∙9H2O溶于乙二醇制成2.5mmol/L的Fe(NO3)3溶液,然后将Fe(NO3)3溶液均匀滴涂到多孔Ni-Cu-La-P合金条带表面,然后在80℃真空干燥箱中烘干,重复上述涂滴过程5次后,在马弗炉中以1℃/min升温速度升温至500℃处理3 h,得到负载纳米γ-Fe2O3的多孔Ni-Cu-La-P电极;
(6)使用三电极体系,将制得的负载纳米γ-Fe2O3的多孔Ni-Cu-La-P薄片作为工作电极,铂电极为辅助电极,饱和甘汞电极为参比电极,电解质溶液为7.5mmol/LMnSO4+0.1mol/LH2SO4溶液,采用循环伏安法在多孔Ni-Cu-La-P合金电极上电沉积SnO2颗粒,扫描范围为-1.5-1.0V,扫描速率10mV/s,扫描圈数为40圈;用去离子水除去电极表面多余的杂质,在80℃干燥5h,然后再300℃下烧结3h,制得γ-Fe2O3/SnO2修饰得多孔Ni-Cu-La-P合金电极;
所制的多孔电极片宽2-5mm,厚35μm,比表面积85m3/g,孔径尺寸为100-300nm;在室温下,将制备γ-Fe2O3/SnO2修饰得多孔Ni-Cu-La-P合金电极作为工作电极进行电化学测试,结果表明,在电流密度为150mA/cm3时,析氢起始电位为-1.48V,析氢过电位为90mV;将本实施例电极用于含微塑料的卡马西平废水的处理,其中微塑料PC含量为0.5mg/L,粒径小于5mm,有机物的初始含量1mg/L,将制备的多孔电极作为阴极,不锈钢电极做阳极,施加1.32V电压,在此电压作用下阴极开始产氢,同时在电极上方施加290nm荧光灯,产生紫外辐射,在此条件下处理10h后,经检测有机废水中卡马西平浓度为0.02mg/L,降解率达到98%,PC含量仅0.02mg/L,降解率达到96%,且电极工作10h后,性能依旧稳定,说明电极材料具有较强的稳定性。
实施例3:本实施例多孔合金电极的制备方法如下:
(1)将质量百分比75%Al粉、7.5%Ni粉、13.7% Cu粉、3%P粉、0.8%La粉的比例将上述粉末加入真空球磨罐内,通入N2,将球磨罐放进球磨机中,球料质量比为6:1,转数为100r/min,每运行30min,间隙12min,总时长100min;
(2)采用等静压机进行压制,将混合物料放入直径15mm模具中,在18MPa下压制25min成型得到直径15mm的粗胚,将粗胚置于刚玉坩埚中,然后置于真空高频感应熔炼炉中熔炼,在Ar气氛、900℃下保温4h,将熔炼后的合金取出冷却后,线切割成1cm3的小正方体块状,打磨表面氧化层;
(3)将小方块放入石英管中并置于真空甩带机中,加热熔化金属,在石英管上方通入0.12-0.15MPa氩气,使呈液态的合金由石英管末端喷出至25r/s的铜辊上,合金溶液与铜辊接触并被甩出发生快速凝固,形成Ni-Cu-La-P-Al合金条带;
(4)将合金条带置于质量浓度40%的NaOH溶液中,在65℃下进行脱Al处理12h,获得多孔Ni-Cu-La-P合金条带,合金条带用去离子水和乙醇洗涤至中性,65℃干燥5h后;
(5)先采用滴涂法将纳米γ-Fe2O3负载到多孔合金电极上,具体是将Fe(NO3)3∙9H2O溶于乙二醇制成3mmol/L的Fe(NO3)3溶液,然后将Fe(NO3)3溶液均匀滴涂到多孔Ni-Cu-La-P合金条带表面,然后在80℃真空干燥箱中烘干,重复上述涂滴过程5次后,在马弗炉中以1℃/min升温速度升温至500℃处理3h,得到负载纳米γ-Fe2O3的多孔Ni-Cu-La-P电极;
(6)使用三电极体系,将制得的负载纳米γ-Fe2O3的多孔Ni-Cu-La-P薄片作为工作电极,铂电极为辅助电极,饱和甘汞电极为参比电极,电解质溶液为7mmol/LMnSO4+0.1mol/LH2SO4溶液,采用循环伏安法在多孔Ni-Cu-La-P合金电极上电沉积ZnO2颗粒,扫描范围为-0.9-1.1V,扫描速率10mV/s,扫描圈数为60圈;用去离子水除去电极表面多余的杂质,在80℃干燥5h,然后再300℃下烧结3h,制得γ-Fe2O3/ZnO2修饰得多孔Ni-Cu-La-P合金电极;
所制的多孔电极片宽2-5mm,厚30μm,比表面积114m3/g,孔径尺寸为100-300nm;在室温下,将制备γ-Fe2O3/ZnO2修饰得多孔Ni-Cu-La-P合金电极作为工作电极进行电化学测试,结果表明,在电流密度为150mA/cm3时,析氢起始电位为-1.47V,析氢过电位为100mV;将本实施例电极用于含微塑料的苯酚废水的处理,其中微塑料PMMA含量为0.5mg/L,粒径小于5mm,有机物的初始含量1mg/L,将制备的多孔电极作为阴极,不锈钢电极做阳极,施加1.33V电压,在此电压作用下阴极开始产氢,同时在电极上方施加310nm荧光灯,产生紫外辐射,在此条件下处理10h后,经检测有机废水中苯酚浓度为0.04mg/L,降解率达到96%,PMMA含量仅0.03mg/L,降解率达到94%,且电极工作10h后,性能依旧稳定,说明电极材料具有较强的稳定性。
Claims (4)
1.一种多孔合金电极的制备方法,其特征在于,步骤如下:
(1)将质量百分比50%-80%Al粉、7.5%-25%Ni粉、5%-15% Cu粉、2%-4%P粉、0.5%-1%La粉加入真空球磨罐内,在N2气氛下球磨混料100-120min;
(2)将混合物料放入模具中,在10-20MPa下压制成型得到粗胚,将粗胚置于刚玉坩埚中,然后置于真空高频感应熔炼炉中熔炼,在Ar气氛、850-900℃下保温2-8h,将熔炼后的合金取出冷却后,切割分成小块,打磨表面氧化层备用;
(3)将切割后的合金小块放入真空甩带机中,制得宽度为2-5mm,厚度为20-50μm的Ni-Cu-La-P-Al合金条带;
(4)将合金条带置于质量浓度20%-45%的NaOH溶液中,在40-80℃下进行脱Al处理12-48h,获得多孔Ni-Cu-La-P合金条带,合金条带用去离子水和乙醇洗涤至中性,干燥后;
(5)先采用滴涂法将纳米γ-Fe2O3负载到多孔合金电极上,再采用电沉积法在多孔合金电极上表面负载BiOX、MnO2、ZnO、SnO2、ZrO2、CdS中的一种,其中X为卤素,制得多孔合金电极。
2.根据权利要求1所述的多孔合金电极的制备方法,其特征在于:Ni粉的粒径<20μm,Al粉的粒径<20μm,La粉的粒径<10μm,Cu粉的粒径<20μm,P粉粒径<10μm。
3.根据权利要求1所述的多孔合金电极的制备方法,其特征在于:真空球磨罐中球料质量比为4-6:1,转数为80-200r/min,每运行15-45min,间隙10-15min。
4.权利要求1-3任一项所述的多孔合金电极的制备方法制得的多孔合金电极在光照条件下处理含微塑料的有机废水且降低析氢过电位中的应用。
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