CN111250106A - 一种花状纳米钯/泡沫镍催化材料的制备方法及其电催化还原脱氯反应的应用 - Google Patents
一种花状纳米钯/泡沫镍催化材料的制备方法及其电催化还原脱氯反应的应用 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 156
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 78
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 57
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title claims description 45
- 238000010531 catalytic reduction reaction Methods 0.000 title description 4
- 239000000243 solution Substances 0.000 claims abstract description 46
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical group 0.000 claims abstract description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
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- 235000020679 tap water Nutrition 0.000 claims abstract description 6
- 238000011549 displacement method Methods 0.000 claims abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000460 chlorine Substances 0.000 claims description 24
- 229910052801 chlorine Inorganic materials 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 235000002639 sodium chloride Nutrition 0.000 claims description 16
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- 238000004140 cleaning Methods 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
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- 239000005416 organic matter Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- OVSKIKFHRZPJSS-DOMIDYPGSA-N 2-(2,4-dichlorophenoxy)acetic acid Chemical compound OC(=O)[14CH2]OC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-DOMIDYPGSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
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- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000006042 reductive dechlorination reaction Methods 0.000 claims 3
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 abstract description 15
- HXKWSTRRCHTUEC-UHFFFAOYSA-N 2,4-Dichlorophenoxyaceticacid Chemical compound OC(=O)C(Cl)OC1=CC=C(Cl)C=C1 HXKWSTRRCHTUEC-UHFFFAOYSA-N 0.000 abstract description 15
- 239000007772 electrode material Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000008151 electrolyte solution Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 230000000382 dechlorinating effect Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- -1 chloroethylene, trichloroethylene, tetrachloroethylene Chemical group 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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Abstract
本发明公开了一种花状纳米钯/泡沫镍电催化材料的制备方法及其电催化还原脱氯反应的应用。以泡沫镍为基底材料,氯化钯溶液为反应溶液,通过化学置换法制备出花状纳米钯/泡沫镍电催化材料。将制备的该材料应用到一氯乙酸和2,4‑二氯苯氧乙酸脱氯,在H型三电极体系中进行,以制备的该电极材料为工作电极,铂为对电极,饱和甘汞电极为参比电极,该体系的阴极室溶液为钠盐溶液、河水或自来水和一氯乙酸或2,4‑二氯苯氧乙酸脱氯,阳极室溶液为钠盐溶液、河水或自来水,在恒电位脱氯法或恒电流脱氯法下脱氯反应1‑3h,一氯乙酸或2,4‑二氯苯氧乙酸转化率达90.0%以上。本发明具有电极材料制备方法简单,脱氯效率高,脱氯反应的电解质溶液来源广的特点。
Description
技术领域
本发明属于电极材料制备技术领域,具体涉及一种花状纳米钯/泡沫镍催化材料的制备方法及其电催化还原脱氯反应的应用。
背景技术
含氯有机物是指有机物分子结构中的氢原子被氯原子取代以后的有机化合物,主要包括氯代脂肪烃、氯代芳香烃及其衍生物。二十世纪,氯代有机物大量生产并广泛应用于农业、染整行业、化工、生物医药及电子等领域。大部分的含氯有机物性质稳定,在自然环境中难以生物降解,在水、土壤和生物体内都有一定的积累。目前我国某些地区含氯有机物的浓度已超出环境的标准要求,对人体健康和环境安全造成严重威胁。含氯有机物导致的环境问题已引起研究者的广泛关注和重视。
对于含氯有机物的脱氯处理,国内外学者做了大量地研究,处理方法有物理法、化学法、生物法、光化学脱氯和电催化还原脱氯法等。其中电催化还原脱氯法被认为是一种处理含氯有机物废水的最有效方法之一,它具有反应条件温和,反应速度快,无二次污染等优点。电极基底材料是影响电催化还原脱氯效率的重要因素,各种常见的电极材料中,具有三维结构的泡沫镍因其较大的比表面积,多孔结构和优异的导电性等优点,被广泛用作电极材料。各种催化材料中,贵金属钯是一种电还原脱氯活性极高的催化材料,因此钯/泡沫镍电极材料被广泛用于含氯有机物的电催化还原脱氯。而目前用来处理含氯有机物电催化还原脱氯技术存在脱氯效率不够高、催化材料成本高和能耗大等不足。国内外环保研究人员正在不懈努力,解决含氯有机物电催化还原脱氯技术中存在的问题。
公开号为CN101074133A的中国发明专利公开了一种工业废水中氯代烃脱氯的工艺,该工艺适用于工业废水中氯代烃的脱氯,适于处理的氯代烃包括二氯甲烷、三氯甲烷、四氯化碳、氯乙烯、三氯乙烯、四氯乙烯等,且脱氯需要时间比较长,本方法没有涉及到有含氯芳香类污染物的脱氯。公开号为CN101565356A的中国发明专利公开了一种氯代苯酚低温脱氯的方法,该方法是用钯炭催化剂对氯代苯酚脱氯,脱氯效率高,但是需要考虑催化剂与反应物和产物的分离,催化剂还需要不断活化处理。公开号为CN102658127A的中国发明专利公开了一种1,2-二氯乙烷选择性加氢脱氯催化剂及其制备方法和应用,该催化材料的制备技术相对比较复杂。
发明内容
鉴于现有技术存在的问题,本发明的目的在于提供了一种花状纳米钯/泡沫镍催化材料的制备方法,并将制备的该材料应用到含氯有机物的脱氯处理。本发明能有效提高脱氯效率,减少贵金属的投入量,催化电极与反应物快速分离,能用于多种电解质溶液和自然水体中含氯有机物的脱氯处理。
所述的一种花状纳米钯/泡沫镍催化材料的制备方法,其特征在于包括如下步骤:
1)先将泡沫镍电极放入丙酮中进行超声波除油,然后放入稀硫酸中浸泡除去表面氧化物,接着在蒸馏水中超声振荡清洗,最后利用高纯氮气将其吹干保存备用;
2)将步骤1)中处理好的泡沫镍电极放入到氯化钯溶液中,通过置换法制备出花状纳米钯/泡沫镍催化材料。
所述的一种花状纳米钯/泡沫镍催化材料的制备方法,其特征在于所述步骤2)具体为:将步骤1)中处理好的泡沫镍电极放入氯化钯溶液中反应,反应温度为25℃-40℃,反应时间为0.5h-2.0h,待反应结束,取出材料经洗涤后用氮气吹干,即得到所要制备的材料。
所述的一种花状纳米钯/泡沫镍催化材料的制备方法,其特征在于所述氯化钯溶液为氯化钯和氯化钠组成的混合溶液,氯化钯与氯化钠溶液络合反应生成易溶于水的氯钯酸钠溶液,所述氯化钯在混合溶液的浓度为0.25-5mmol/L,其中氯化钯和氯化钠物质的量之比为1:3-1:500。
所述的一种花状纳米钯/泡沫镍催化材料的制备方法,其特征在于所述步骤1)中稀硫酸的浓度为0.5mol/L,所述制备出的材料中泡沫镍表面钯载量为0.1-1.0mg/cm2。
所述方法制备的花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述制备的花状纳米钯/泡沫镍催化材料作为工作电极在H型三电极体系里通过电化学脱氯法对含氯有机物脱氯处理。
所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于在H型三电极体系中,所述制备的花状纳米钯/泡沫镍催化材料为工作电极,饱和甘汞电极为参比电极,铂电极为对电极,阴极室和阳极室之间用Nafion-117阳离子交换膜隔开,该体系的阴极室溶液为含氯有机物和钠盐溶液、河水或自来水组成的的混合溶液,阳极室溶液为钠盐溶液、河水或自来水,在反应温度为5-35℃,反应时间为1-3h条件下,对含氯有机物进行脱氯。
所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述电化学脱氯法为恒电流脱氯法或恒电位脱氯法。
所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述含氯有机物为一氯乙酸或2,4-二氯苯氧乙酸,且含氯有机物浓度为0.01-0.4mmol/L。
所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述钠盐溶液为硫酸钠、碳酸氢钠、氯化钠及高氯酸钠中的一种或两种,且钠盐溶液浓度为10-100mmol/L。
所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述阴极室溶液流速为5.0ml/min-50.0ml/min,阴极室溶液反应前pH值为2.5-10。
本发明的脱氯原理为:
花状纳米钯/泡沫镍电极表面的活性位点吸附活性氢,活性氢进攻含氯有机物中C-Cl键,发生还原反应,使Cl原子脱除。反应式为:
H2O+e-+Pd→[H]adsPd+OH-(中性和碱性溶液)或
H++e-+Pd→(H)adsPd(酸性溶液)(1)
(R-Cl)ads Pd+2[H]adsPd→(R-H)ads Pd+HCl+Pd(3)
其中(1)-(4)是本发明脱氯处理的主反应,脱氯反应是不断重复(1)-(4)这四个步骤,直到含氯有机物上的氯被全部脱除。Pd代表催化电极表面有吸附活性的钯活性位;R-Cl代表含氯有机物;(R-Cl)adsPd代表钯电极表面吸附的含氯有机物;[H]ads Pd代表电极表面钯吸附的活性氢。
与现有技术相比较,本发明的有益效果:
1)本发明花状纳米钯/泡沫镍电催化材料制备方法简单、绿色环保;
2)采用本发明的技术方案对一氯乙酸或2,4-二氯苯氧乙酸脱氯处理,脱氯效率高,电极材料成本低,反应条件温和,二次污染少,电解质溶液来源广,一氯乙酸和2,4-二氯苯氧乙酸的去除效率能达到90.0%以上。
具体实施方式
下面结合实施例对本发明作进一步的说明,但本发明所保护的范围不局限于所述范围。
实施例1
先将泡沫镍(2cm*2cm*1.2cm)电极放入丙酮中进行超声波除油,然后放入0.5mol/L的稀硫酸中浸泡除去表面氧化物,接着在蒸馏水中超声振荡清洗,最后利用高纯氮气将其吹干保存备用。
取一片洗净的泡沫镍(2cm*2cm*1.2cm)放入40ml 0.25mmol/L的氯化钯溶液(氯化钯在混合溶液的浓度)中,氯化钯和氯化钠物质的量之比为1:500,在25℃,转速160次/分的摇床里反应0.5h,溶液的浅黄色退去,取出电极用去离子水轻轻的冲洗3次,用氮气吹干,制备出花状纳米钯/泡沫镍催化电极为工作电极待用。脱氯反应为H型三电极体系:将制备的花状纳米钯/泡沫镍电极作为工作电极,饱和甘汞电极为参比电极,铂电极为对电极;阴极溶液的流速为5.0ml/min;阴极电解液为10mmol/L碳酸氢钠和0.01mmol/L 2,4-二氯苯氧乙酸的混合溶液,阳极电解液为10mmol/L的碳酸氢钠溶液;采用恒电位脱氯法对2,4-二氯苯氧乙酸脱氯,反应时间为3h,反应结束后,2,4-二氯苯氧乙酸的去除效率为90.5%。
实施例2
先将泡沫镍(2cm*2cm*1.2cm)电极放入丙酮中进行超声波除油,然后放入0.5mol/L的稀硫酸中浸泡除去表面氧化物,接着在蒸馏水中超声振荡清洗,最后利用高纯氮气将其吹干保存备用。
取一片洗净的泡沫镍(2cm*2cm*1.2cm)放入40ml 0.5mmol/L的氯化钯溶液(氯化钯在混合溶液的浓度)中,氯化钯和氯化钠物质的量之比为1:100,在40℃,转速160次/分的摇床里反应2h,溶液的浅黄色退去,取出电极用去离子水轻轻的冲洗3次,用氮气吹干,制备出花状纳米钯/泡沫镍催化电极为工作电极待用。脱氯反应为H型三电极体系:将制备的花状纳米钯/泡沫镍电极作为工作电极,饱和甘汞电极为参比电极,铂电极为对电极;阴极溶液的流速为25ml/min;阴极电解液为0.225mmol/L的2,4-二氯苯氧乙酸和40mmol/L的氯化钠的混合溶液,阳极电解液为40mmol/L的氯化钠溶液;采用恒电位脱氯法对2,4-二氯苯氧乙酸脱氯,反应时间为3h,反应结束后,2,4-二氯苯氧乙酸的去除效率为99.5%以上。
实施例3
先将泡沫镍(2cm*2cm*1.2cm)电极放入丙酮中进行超声波除油,然后放入0.5mol/L的稀硫酸中浸泡除去表面氧化物,接着在蒸馏水中超声振荡清洗,最后利用高纯氮气将其吹干保存备用。
取一片洗净的泡沫镍(2cm*2cm*1.2cm)放入40ml 2mmol/L的氯化钯溶液(氯化钯在混合溶液的浓度)中,氯化钯和氯化钠物质的量之比为1:100,在30℃,转速160次/分的摇床里反应2h,溶液的浅黄色退去,取出电极用去离子水轻轻的冲洗3次,用氮气吹干,制备出花状纳米钯/泡沫镍催化电极为工作电极待用。脱氯反应为H型三电极体系:将制备的花状纳米钯/泡沫镍电极作为工作电极,饱和甘汞电极为参比电极,铂电极为对电极;阴极溶液的流速为25ml/min;阴极电解液为20mmol/L碳酸氢钠和0.4mmol/L 2,4-二氯苯氧乙酸的混合溶液,阳极电解液为20mmol/L的碳酸氢钠溶液;采用恒电位脱氯法对2,4-二氯苯氧乙酸脱氯,反应时间为3h,反应结束后,2,4-二氯苯氧乙酸的去除效率为93.9%以上。
实施例4
先将泡沫镍(2cm*2cm*1.2cm)电极放入丙酮中进行超声波除油,然后放入0.5mol/L的稀硫酸中浸泡除去表面氧化物,接着在蒸馏水中超声振荡清洗,最后利用高纯氮气将其吹干保存备用。
取一片洗净的泡沫镍(2cm*2cm*1.2cm)放入40ml 0.5mmol/L的氯化钯溶液(氯化钯在混合溶液的浓度)中,氯化钯和氯化钠物质的量之比为1:500中,在30℃,转速160次/分的摇床里反应2h,溶液的浅黄色退去,取出电极用去离子水轻轻的冲洗3次,用氮气吹干,制备出花状纳米钯/泡沫镍催化电极为工作电极待用。脱氯反应为H型三电极体系:将制备的花状纳米钯/泡沫镍电极作为工作电极,饱和甘汞电极为参比电极,铂电极为对电极;阴极溶液的流速为50ml/min;阴极电解液为0.225mmol/L的2,4-二氯苯氧乙酸和40mmol/L的碳酸氢钠的混合溶液,阳极电解液为40mmol/L的碳酸氢钠溶液;采用恒电流脱氯法对2,4-二氯苯氧乙酸脱氯,反应时间为1h,反应结束后,2,4-二氯苯氧乙酸的去除效率为99.5%以上。
实施例5
先将泡沫镍(2cm*2cm*1.2cm)电极放入丙酮中进行超声波除油,然后放入0.5mol/L的稀硫酸中浸泡除去表面氧化物,接着在蒸馏水中超声振荡清洗,最后利用高纯氮气将其吹干保存备用。
取一片洗净的泡沫镍(2cm*2cm*1.2cm)放入40ml 0.5mmol/L的氯化钯溶液(氯化钯在混合溶液的浓度)中,氯化钯和氯化钠物质的量之比为1:3,在30℃,转速160次/分的摇床里反应1.0h,溶液的浅黄色退去,取出电极用去离子水轻轻的冲洗3次,用氮气吹干,制备出花状纳米钯/泡沫镍催化电极为工作电极待用。脱氯反应为H型三电极体系:将制备的花状纳米钯/泡沫镍电极作为工作电极,饱和甘汞电极为参比电极,铂电极为对电极;阴极溶液的流速为25ml/min;阴极电解液为0.225mmol/L的一氯乙酸和100mmol/L的氯化钠的混合溶液,阳极电解液为100mmol/L的氯化钠溶液;采用恒电流脱氯法对一氯乙酸脱氯,反应时间为2h,反应结束后,一氯乙酸的去除效率为99.5%以上。
实施例6
先将泡沫镍(2cm*2cm*1.2cm)电极放入丙酮中进行超声波除油,然后放入0.5mol/L的稀硫酸中浸泡除去表面氧化物,接着在蒸馏水中超声振荡清洗,最后利用高纯氮气将其吹干保存备用。
取一片洗净的泡沫镍(2cm*2cm*1.2cm)放入40ml 5mmol/L的氯化钯溶液(氯化钯在混合溶液的浓度)中,氯化钯和氯化钠物质的量之比为1:100,在30℃,转速160次/分的摇床里反应2h,溶液的浅黄色退去,取出电极用去离子水轻轻的冲洗3次,用氮气吹干,制备出花状纳米钯/泡沫镍催化电极为工作电极待用。脱氯反应为H型三电极体系:将制备的花状纳米钯/泡沫镍电极作为工作电极,饱和甘汞电极为参比电极,铂电极为对电极;阴极溶液的流速为25ml/min;阴极电解液为0.01mmol/L的2,4-二氯苯氧乙酸和河水的混合溶液,阳极电解液为河水;采用恒电流脱氯法对2,4-二氯苯氧乙酸脱氯,反应时间为2h,反应结束后,2,4-二氯苯氧乙酸的去除效率为99.5%以上。
Claims (10)
1.一种花状纳米钯/泡沫镍催化材料的制备方法,其特征在于包括如下步骤:
1)先将泡沫镍电极放入丙酮中进行超声波除油,然后放入稀硫酸中浸泡除去表面氧化物,接着在蒸馏水中超声振荡清洗,最后利用高纯氮气将其吹干保存备用;
2)将步骤1)中处理好的泡沫镍电极放入到氯化钯溶液中,通过置换法制备出花状纳米钯/泡沫镍催化材料。
2.根据权利要求1所述的一种花状纳米钯/泡沫镍催化材料的制备方法,其特征在于所述步骤2)具体为:将步骤1)中处理好的泡沫镍电极放入氯化钯溶液中反应,反应温度为25-40℃,反应时间为0.5-2.0h,待反应结束,取出材料经洗涤后用氮气吹干,即得到所要制备的材料。
3.根据权利要求1或2所述的一种花状纳米钯/泡沫镍催化材料的制备方法,其特征在于所述氯化钯溶液为氯化钯和氯化钠组成的混合溶液,氯化钯与氯化钠溶液络合反应生成易溶于水的氯钯酸钠溶液,所述氯化钯在混合溶液的浓度为0.25-5mmol/L,其中氯化钯和氯化钠物质的量之比为1:3-1:500。
4.根据权利要求1所述的一种花状纳米钯/泡沫镍催化材料的制备方法,其特征在于所述步骤1)中稀硫酸的浓度为0.5mol/L,所述制备出的材料中泡沫镍表面钯载量为0.1-1.0mg/cm2。
5.一种根据权利要求1所述方法制备的花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述制备的花状纳米钯/泡沫镍催化材料作为工作电极在H型三电极体系里通过电化学脱氯法对含氯有机物脱氯处理。
6.根据权利要求5所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于在H型三电极体系中,所述制备的花状纳米钯/泡沫镍催化材料为工作电极,饱和甘汞电极为参比电极,铂电极为对电极,阴极室和阳极室之间用Nafion-117阳离子交换膜隔开,该体系的阴极室溶液为含氯有机物和钠盐溶液、河水或自来水组成的的混合溶液,阳极室溶液为钠盐溶液、河水或自来水,在反应温度为5-35℃,反应时间为1-3h条件下,对含氯有机物进行脱氯。
7.根据权利要求5所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述电化学脱氯法为恒电流脱氯法或恒电位脱氯法。
8.根据权利要求5或6所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述含氯有机物为一氯乙酸或2,4-二氯苯氧乙酸,且含氯有机物的浓度为0.01-0.4mmol/L。
9.根据权利要求6所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述钠盐溶液为硫酸钠、碳酸氢钠、氯化钠及高氯酸钠中的一种或两种,且钠盐溶液浓度为10-100mmol/L。
10.根据权利要求6所述的一种花状纳米钯/泡沫镍催化材料在电催化还原脱氯反应的应用,其特征在于所述阴极室溶液流速为5.0-50.0ml/min,阴极室溶液反应前pH值为2.5-10。
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