CN114182269B - 一种电化学还原脱氯转化含氯挥发性有机物的方法 - Google Patents
一种电化学还原脱氯转化含氯挥发性有机物的方法 Download PDFInfo
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- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 26
- -1 hydrogen ions Chemical class 0.000 claims abstract description 32
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明提供一种电化学还原脱氯转化含氯挥发性有机物的方法,所述方法为:以含有0.01~2mol/L含氯挥发性有机物的碱性溶液为阴极液置于所述阴极电解室,以含0.1~5mol/L氢离子、锂离子、四甲基铵根离子或四乙基铵根离子中至少一种阳离子的水溶液为阳极液置于所述阳极电解室,在电流密度为0.5~20A/dm2下通电进行电解;与现有技术相比,本发明特定的阴极液配方和阴极材料使得Cl‑VOCs电化学还原脱氯体系脱氯效率更高,阳极液配方使得Cl‑VOCs电化学还原脱氯体系能转化更高浓度的Cl‑VOCs。
Description
(一)技术领域
本发明属于电化学脱氯技术领域,涉及含氯挥发性有机物(Cl-VOCs)的脱氯转化方法,具体涉及一种电化学还原脱氯转化Cl-VOCs的方法。
(二)技术背景
氯代挥发性有机化合物(Cl-VOCs),包括多氯甲烷、多氯乙烷、多氯乙烯和含氯氟利昂,被广泛用作溶剂、脱脂剂、制冷剂和各种商业产品。多数Cl-VOCs毒性较高,不仅具有三致效应而且较难自然降解。另外,其进入大气会破坏大气层中的臭氧层或者延缓大气层中臭氧层的自我修复。因此,大部分Cl-VOCs被美国环保署和中国环境局列为优先控制污染物。含氯VOCs对人类的毒性、生态环境的危害性和难降解性主要源于其分子上的氯原子,如能将氯原子选择性脱除,生成的无氯产物可作为原料回收或者作为燃料利用。因此,开发高效、环境友好的Cl-VOCs选择性脱氯技术是环境保护领域热门课题,受到了国内外学者的广泛关注。
Cl-VOCs的选择性脱氯方法主要包括:以LiAlH4和NaBH4为还原剂的化学脱氯法,零价金属还原脱氯法、贵金属催化加氢脱氯法,生物还原脱氯法和电化学氢化脱氯法。以LiAlH4和NaBH4为还原剂的脱氯法因其所用还原剂价格过高而不适合大规模使用。零价金属脱氯法以铁、锌等零价金属为还原剂,具有价格低、操作便捷的优点,但此方法存在着脱氯不彻底和产生大量废渣的缺点。贵金属催化加氢脱氯法以铂、钯、铑等贵金属为催化剂,氢气为还原剂,具有反应速度快、脱氯彻底的优点,其应用主要受催化剂价格过于昂贵和氢气储存与运输困难的限制。生物还原脱氯法具有投资少、运行费用低等优点,但存在对于成分复杂、波动性大、水溶性差、不易生物降解的Cl-VOCs,去除效果较差的问题。
与上述脱氯方法相比,以电子为还原剂的电化学氢化脱氯法具有能以水为氢供体、可常温常压下进行和脱氯彻底高效的优点。因此,近年来Cl-VOCs的电化学氢化脱氯方法受到了国内外环境科学家广泛地研究。电化学氢化脱氯可在水相中进行,也可以在有机溶剂中进行。其中,水相中的电化学氢化脱氯主要用于低浓度Cl-VOCs的直接处理。而有机溶剂中的电化学氢化脱氯不仅可用于转化现有的已被禁止的Cl-VOCs或在某些工业过程中作为副产品产生的Cl-VOCs从而实现变废为宝,而且还能用于废气中或者废水中低浓度Cl-VOCs的间接处理(一旦这些物质通过活性炭吸附或者空气吹脱从水中提取,或者通过有机溶剂从废气中吸收富集)。另外,有机溶剂中的电化学氢化脱氯可在高浓度底物条件下进行,相比用于低浓度Cl-VOCs直接处理的水相中电化学氢化脱氯具有更加高效的优点。因此,有机溶剂中Cl-VOCs的电化学氢化脱氯方法具有更广阔的应用前景。
在有机溶剂中Cl-VOCs的电化学氢化脱氯方面,目前大部分研究为基础理论研究,目标为实际工业应用的研究报道较为少见。根据意大利Armando Gennaro教授团队的报道,以含有乙酸和四丁基高氯酸铵的DMF溶液为阴极液,氯甲烷在石墨和银电极上能转化成甲烷[Applied Catalysis B:Environmental 88(2009)479–489];以含乙酸(或水)和四丁基四氟硼酸铵的DMF溶液为阴极液,氯乙烷和三氯乙烯在铜电极上也都能彻底氢化脱氯[Applied Catalysis B:Environmental 126(2012)355–362]。遗憾的是,这些报道并没有标明阳极液的组成,因此无法判断在电解脱氯反应中,阴极液组份的变化;另外,这些报道的阴极液中Cl-VOCs的浓度都比较低(10mM)。根据意大利Sandra Rondinini教授团队的报道,以硫酸钠水溶液为阳极液,以含四乙基四氟硼酸铵的乙腈/水(体积比为1:1)混合溶液为阴极液,三氯甲烷能在银电极上转化成甲烷[Electrochimica Acta 49(2004)4035–4046];以硫酸钠水溶液为阳极液,以含四乙基四氟硼酸铵的乙腈溶液为阴极液,三氯甲烷能在银电极上转化成甲烷[Journal of Applied Electrochemistry(2005)35:363–368]。遗憾的是,这两个报道中Cl-VOCs的转化率都比较低,分别为80%和20%。中国发明专利202010260946.7和202010260938.2报道了以碱性水溶液为阳极液,酸性有机溶液为阴极液的二氯甲烷电化学还原转化成甲烷的方法。该方法存在电流效率偏低的问题。
(三)发明内容
本发明目的是针对现有技术在转化率低、电流效率低等方面的不足,提供一种电化学还原脱氯转化含氯挥发性有机物(Cl-VOCs)的方法。
为了实现上述目的,本发明的具体方案如下:
本发明提供一种电化学还原脱氯转化含氯挥发性有机物(Cl-VOCs)的方法,所述电化学还原脱氯在双室电解池中进行,所述电解池包括内置阴极的阴极电解室、内置阳极的阳极电解室及分隔所述阴极电解室与阳极电解室的隔膜;所述阴极的表面包含银、铜、铅、锡或铋中至少一种金属;所述隔膜为阳离子隔膜;
所述方法为:以含有0.01~2mol/L(优选0.1~1mol/L)含氯挥发性有机物的碱性溶液为阴极液置于所述阴极电解室,以含氢离子、锂离子、四甲基铵根离子或四乙基铵根离子中至少一种阳离子的水溶液为阳极液置于所述阳极电解室,在电流密度为0.5~20A/dm2下通电进行电解;
所述电解的时间为理论所需电解时间的0.9~10倍(优选1.17~2.1倍),设所述理论所需电解时间为t,单位为秒:
t=F×2N/I
其中,F为法拉第常数,单位为C/mol,N为所述含氯挥发性有机物的碱性溶液中所含氯原子的理论物质的量,单位为mol;I为所述电解的电流大小,单位为A;
理论时间的0.9倍即可达到转化率大于80%,继续延长反应时间Cl-VOCs转化率可大于95%。反应时间过长电流效率会降低。I=电流密度×所述阴极的投影面积;
所述阴极液还含0.001~5mol/L(优选0.001~1mol/L)水和0.001~5mol/L(优选0.1~0.5mol/L)碱性物质;所述碱性物质为氢氧化锂、四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵或四丁基氢氧化铵中的一种或两种以上的混合物,所述阴极液的溶剂为与水互溶的极性有机溶剂;所述阳离子的水溶液中阳离子的浓度为0.1~5mol/L(优选1~2mol/L)。初始阴极液中对水的需求极少,因为后续在阳极液中的水会不断进入阴极液中。阳极液为碱性水溶液时(例如氢氧化锂水溶液为阳极液),初始阴极液可以为中性(不含碱性物质)甚至为弱酸性。因为随着电解的进行,阳极液中的锂离子、四甲基铵根离子或四乙基铵根离子会不断进入阴极液中,从而使阴极液转变成碱性。
具体地,所述的阳离子膜,可以是任何种类的阳离子交换膜,但需要阳离子交换膜不被电解液中的有机溶剂和Cl-VOCs溶解,例如可以使用全氟磺酸阳离子交换膜,本发明推荐Nafion 324阳离子膜。
所述有机溶剂为能与水互溶的极性有机溶剂,例如乙腈、DMF、DMSO、丙酮等非质子溶剂,甲醇、乙醇等醇类有机溶剂;所述碱性溶液中的有机溶剂也可以上述溶剂的混合体,例如体积比为1:1的甲醇和乙腈的混合溶剂,优选DMF、乙腈、DMSO、甲醇或乙醇。
进一步优选地,当所述碱性物质为氢氧化锂,所述有机溶剂为醇类有机溶剂(如甲醇或乙醇)时,还可以向所述阴极液中加入终浓度为0.01~1mol/L(优选0.1mol/L)的铵根离子,所述铵根离子为四甲基铵根离子、四乙基铵根离子、四丙基铵根离子、四丁基铵根离子中一种或两种以上的混合物(优选以四丁基四氟硼酸铵、四乙基氢氧化铵或四丁基氢氧化铵的形式加入),进一步促进反应。
优选地,所述阴极液中含氯挥发性有机物是氯甲烷、氯乙烷、氯乙烯、含氯氟利昂等中的一种或两种以上的混合物。
进一步,所述的电解的电流密度0.5~20A/dm2,根据不同的Cl-VOCs浓度,优选电流密度是不同的,对于Cl-VOCs的优选浓度(0.1~1mol/L),对应的优选电流密度为3~10A/dm2;为了提高电流效率也可以在电解后期降低电解的电流密度;所述电流密度以阴极的投影面积进行计算所得。
进一步,所述的电解的温度为0~80℃,优选20~50℃。
所述电解的阴极上至少包含银或铜或铅或锡或铋等金属,这些金属材料需要处于电极的表面,可以电沉积、化学置换、化学沉积、涂敷等方法让这些金属处于电极的表面。阴极的基体也可以是这些金属材料,也可以是任何导电性良好,同时耐阴极液腐蚀的材料。例如基体材料可以是Ti和C材料。阴极基体材料可以是任何几何形状的,例如片状、网状、泡沫状等等。优选修饰了银纳米颗粒的导电材料为阴极。
举例来说,本发明采用氧化还原法制备所述阴极材料,所述阴极按如下方法制备:将银网电极依次置于丙酮和浓度为10wt%的盐酸中分别超声清洗10min,得到预处理过的银网电极;然后在H型电解池中(Nafion 117为隔膜),以所述预处理过的银网电极作为工作电极,以银/氯化银作为参比电极,以铂片作为辅助电极,以0.5mol/L NaCl的水溶液为工作电极电解液,0.5mol/L H2SO4的水溶液为辅助电极电解液对所述预处理过的银网电极进行电化学氧化处理,所述电化学氧化处理的电流密度为0.5A/dm2,截止氧化电位为+1.5Vvs.SHE,得到氧化的银网电极;然后调换所述H型电解池的阴阳两极,对所述氧化的银网电极进行电化学还原处理,截止还原电位为-1.5V vs.SHE,得到所述阴极。
上述氧化还原法的反应原理是:将银网表面的金属银氧化成氯化银,然后再还原成金属银。这样处理后,表面的金属银变成银金属纳米颗粒。
所述阳极液中氢离子或锂离子或四甲基铵根离子或四乙基铵根离子的浓度为0.1~5mol/L,优选1~2mol/L。例如,可以硫酸水溶液或者盐酸水溶液等含氢离子的溶液为阳极液,也可以氯化锂水溶液或者四甲基碳酸铵水溶液等中性溶液为阳极液,还可以氢氧化锂或者四甲基氢氧化铵水溶液等碱性溶液为阳极液。
优选地,所述阳极液中,氢离子以硫酸的形式加入,锂离子以氢氧化锂的形式加入,四甲基铵根离子以四甲基氢氧化铵的形式加入,四乙基铵根离子以四乙基氢氧化铵的形式加入。
所述阳极的材料可以根据阳极液适当选择。不同阳极液中选择合适的阳极材料是本专业领域人员容易做到的。例如,以硫酸水溶液为阳极液时,阳极可选择钛基的铂、二氧化铅或者氧化铱涂层作为阳极材料;以氯化物水溶液为阳极液时,可选择钛基氧化钌涂层或者石墨作为阳极材料;以碱性水溶液为阳极液时,可选择不锈钢316等不锈钢作为阳极材料。
与现有技术相比,本发明的有益效果主要体现在:
(1)与现有技术相比,本发明特定的阴极液配方和阴极材料使得Cl-VOCs电化学还原脱氯体系脱氯效率更高(脱氯电流效率、Cl-VOCs转化率和无氯产物的收率分别提高>15.5%,>16.8%和>12.0%)。
(2)与现有技术相比,本发明特定的阳极液配方使得Cl-VOCs电化学还原脱氯体系能转化更高浓度的Cl-VOCs(2mol/L)。
(3)与现有技术相比,本发明特定的电极上Cl-VOCs的还原电位能正向移动约500mV。
(四)附图说明
图1氧化还原处理后银网电极表面的(A)扫描电子显微镜照片、从氧化还原处理后银网电极表面超声清洗下来的(B)银纳米颗粒(Ag NPs)的透射电子显微镜照片以及(C)银纳米粒径分布图和(D)Ag NPs与未经氧化还原处理银网电极的X射线衍射图。
图2带气袋的H型隔膜电解池。
图3氮气气氛中10mmol/L(mM)二氯甲烷在玻碳(GC)、光亮银(Ag(p))和银纳米颗粒修饰银(Ag NPs/Ag)电极上的循环伏安(CV)曲线。(A、D和G)为GC电极上的CV曲线,(B、E和H)为Ag(p)电极上的CV曲线,(C、F和I)为Ag NPs/Ag电极上的CV曲线;(A、B和C)为含0.1mol/L(C4H9)4NBF4、0.2mol/L水和40mmol/L乙酸的DMF溶液中的CV曲线,(D、E和F)为含0.1mol/L(C4H9)4NBF4和0.2mol/L水的DMF溶液中的CV曲线,(G、H和I)为含0.1mol/L(C4H9)4NBF4、0.2mol/L水和40mmol/L氢氧化锂的DMF溶液中的CV曲线。
(五)具体实施方式
下面结合实施例对本发明作进一步说明,本发明的保护范围并不限于此实施例1银纳米颗粒修饰银网电极的制备
首先将银网电极(投影面积:2×3.5cm2)依次置于丙酮和稀盐酸(10wt%)溶液中超声清洗各10min;然后在H型电解池中(Nafion 117为隔膜),分别以银网电极、银/氯化银、铂片作为工作电极、参比电极和辅助电极,0.5mol/L NaCl水溶液为工作电极电解液,0.5mol/LH2SO4水溶液为辅助电极电解液进行电化学氧化还原处理。上述清洗过程和氧化还原处理过程中银网电极的温度都控制在20~25℃。氧化还原处理的电流密度为0.5A/dm2,截止氧化电位为+1.5V vs.SHE截止还原电位为-1.5V vs.SHE。氧化还原过程重复2次后,将银网电极用去离子水冲洗干净,然后置于去离子水中待用。图1分别显示了氧化还原处理后银网电极表面的扫描电子显微镜照片、从氧化还原处理后银网电极表面超声清洗下来的银纳米颗粒(Ag NPs)的透射电子显微镜照片以及银纳米粒径分布图和Ag NPs与未经氧化还原处理银网电极的X射线衍射图。由图可见,氧化还原处理后,银网表面分布了大量直径约为100~300nm的圆球(图1A),这些圆球由大量平均直径大约为7nm的银纳米颗粒组成(图1B、C和D)。
实施例2二氯甲烷的电化学还原脱氯
以如图2所示的带气袋H型电解池为反应器,以Nafion 324阳离子膜为隔膜,投影面积为2×3.5cm2的Ag NPs/Ag网为阴极,2×2cm2的镀铂钛片为阳极。阴极和阳极的距离5cm。50mL含0.1mol/L二氯甲烷+0.22mol/L LiOH+1mol/L水的DMF溶液为阴极液;50mL1mol/L硫酸水溶液为阳极液。电解过程中,温度控制为30~35℃,电流密度控制为3.57A/dm2(电流为250mA),阴极液pH=9.0~12.5。电解3小时后停止电解。用气相色谱分析阴极液和气袋中收集气体中一氯甲烷和甲烷的浓度,然后计算得到:二氯甲烷的转化率为99%,一氯甲烷的收率为0.6%,甲烷的收率为97.1%,电流效率为69.4%。
表1二氯甲烷电化学还原脱氯的条件和结果。除特殊说明外,实施例3~30的条件与实施例2一样。表格中pH值由pH试纸测定;倍数为实际电解时间除以理论电解时间的倍数。
表2不同Cl-VOCs电化学还原脱氯的条件和结果。除特殊说明外,实施例31~33的条件与实施例2一样。表格中pH值由pH试纸测定。
实施例34不同酸碱条件下、不同电极上二氯甲烷的循环伏安图
在50mL带控温夹套和橡皮塞的烧杯中,分别加入30mL含0.1mol/L(C4H9)4NBF4+0.2mol/L水+40mmol/L乙酸、0.1mol/L(C4H9)4NBF4+0.2mol/L水或0.1mol/L(C4H9)4NBF4+0.2mol/L水+40mmol/L LiOH的DMF溶液。三种溶液的pH值分别约为4,7,10(用pH试纸测定)。以投影面积均为3.14mm2玻碳(GC)、光亮银(Ag(p))和银纳米颗粒修饰的银(Ag NPs/Ag)电极为工作电极,以银/银离子(Ag/Ag+)电极和铂片电极分别为参比电极和辅助电极,在加入10mmol/L二氯甲烷前后分别进行循环伏安(CV)测试,结果如图3所示。CV测试的起始电位、扫描速度和测试液温度分别为:-1V vs.Ag/Ag+(含0.1mol/L硝酸银的乙腈溶液)、50mV/s和25℃。CV测试前DMF溶液中用玻璃管通入氮气15min,CV测试过程中通入氮气的玻璃管置于DMF溶液液面之上,橡皮塞之下。由图可见,对于二氯甲烷的还原反应,电极性能从高到底的次序为Ag NPs/Ag>Ag(p)>GC;电解液性能从高到低的次序为:碱性≈中性>酸性。
对比例1二氯甲烷的电化学还原脱氯
以如图2所示的带气袋H型电解池为反应器,以Nafion 324阳离子膜为隔膜,投影面积为2×3.5cm2的Ag NPs/Ag网为阴极,2×2cm2的镀铂钛片为阳极。阴极和阳极的距离5cm。50mL含0.1mol/L二氯甲烷+0.1mol/L(C4H9)4NBF4+0.22mol/L乙酸+1mol/L水的DMF溶液为阴极液;50mL 1mol/L硫酸水溶液为阳极液。电解过程中,温度控制为30~35℃,电流密度控制为3.57A/dm2(电流为250mA),阴极液pH=5.0~2.5。电解3小时后停止电解。用气相色谱分析阴极液和气袋中收集气体中一氯甲烷和甲烷的浓度,然后计算得到:二氯甲烷的转化率为66.4%,一氯甲烷的收率为0.8%,甲烷的收率为63.4%,电流效率为45.4%。
表3二氯甲烷电化学还原脱氯的条件和结果(对比例)。除特殊说明外,对比例2~10的条件与对比例1一样。表格中pH值由pH试纸测定。
Claims (9)
1.一种电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:所述电化学还原脱氯在双室电解池中进行,所述电解池包括内置阴极的阴极电解室、内置阳极的阳极电解室及分隔所述阴极电解室与阳极电解室的隔膜;所述阴极的表面包含银、铜、铅、锡或铋中至少一种金属;所述隔膜为阳离子膜;
所述方法为:以含有0.01~2 mol/L含氯挥发性有机物的碱性溶液为阴极液置于所述阴极电解室,以含氢离子、锂离子、四甲基铵根离子或四乙基铵根离子中至少一种阳离子的水溶液为阳极液置于所述阳极电解室,在电流密度为0.5~20 A/dm2下通电进行电解;
所述电解的时间为理论所需电解时间的0.9~10倍,设所述理论所需电解时间为t,单位为秒:
t=F×2N/I
其中,F为法拉第常数,单位为C/mol,N为所述含氯挥发性有机物的碱性溶液中所含氯原子的理论物质的量,单位为mol;I为所述电解的电流大小,单位为A;
所述阴极液还含0.001~5 mol/L水和0.001~5 mol/L碱性物质;所述碱性物质为氢氧化锂、四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵或四丁基氢氧化铵中的一种或两种以上的混合物,所述阴极液的溶剂为与水互溶的极性有机溶剂;所述阳极液中阳离子的浓度为0.1~5 mol/L;所述阴极液中含氯挥发性有机物是氯甲烷、氯乙烷、氯乙烯、含氯氟利昂中的一种或两种以上的混合物。
2.如权利要求1所述的电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:所述有机溶剂为非质子溶剂或醇类有机溶剂。
3.如权利要求2所述的电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:所述有机溶剂为DMF、乙腈、DMSO、甲醇或乙醇。
4.如权利要求1所述的电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:当所述碱性物质为氢氧化锂,所述有机溶剂为醇类有机溶剂时,所述阴极液中还含终浓度为0.01~1mol/L的铵根离子,所述铵根离子为四甲基铵根离子、四乙基铵根离子、四丙基铵根离子、四丁基铵根离子中一种或两种以上的混合物。
5.如权利要求1所述的电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:所述含氯挥发性有机物的碱性溶液中含氯挥发性有机物的浓度为0.1~1 mol/L,所述的电解的电流密度3~10 A/dm2。
6.如权利要求1所述的电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:所述的电解的温度为0~80℃。
7.如权利要求1所述的电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:以修饰了银纳米颗粒的导电材料为阴极,所述阴极按如下方法制备:将银网电极依次置于丙酮和浓度为10 wt%的盐酸中分别超声清洗10 min,得到预处理过的银网电极;然后在H型电解池中,以所述预处理过的银网电极作为工作电极,以银/氯化银作为参比电极,以铂片作为辅助电极,以0.5 mol/L NaCl的水溶液为工作电极电解液,0.5 mol/L H2SO4的水溶液为辅助电极电解液对所述预处理过的银网电极进行电化学氧化处理,所述电化学氧化处理的电流密度为0.5A/dm2,截止氧化电位为+1.5V vs. SHE,得到氧化的银网电极;然后调换所述H型电解池的阴阳两极,对所述氧化的银网电极进行电化学还原处理,截止还原电位为-1.5V vs. SHE,得到所述阴极。
8.如权利要求1所述的电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:所述阴极液中碱性物质的浓度为0.1~0.5 mol/L。
9.如权利要求1所述的电化学还原脱氯转化含氯挥发性有机物的方法,其特征在于:所述阳极液中,氢离子以硫酸的形式加入,锂离子以氢氧化锂的形式加入,四甲基铵根离子以四甲基氢氧化铵的形式加入,四乙基铵根离子以四乙基氢氧化铵的形式加入。
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