CN106423276A - 一种氮掺杂碳负载镍电Fenton催化剂的制备方法 - Google Patents
一种氮掺杂碳负载镍电Fenton催化剂的制备方法 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 5
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 7
- 229940043267 rhodamine b Drugs 0.000 abstract description 7
- 239000010406 cathode material Substances 0.000 abstract description 5
- -1 aminocarboxylic acid compound Chemical class 0.000 abstract description 2
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
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- 229910002804 graphite Inorganic materials 0.000 description 3
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- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
本发明公开了一种氮掺杂碳负载镍电Fenton催化剂的制备方法，是将碳材前处理后放入马弗炉中，350℃下热处理1h，冷却后浸入镍盐和氨基羧酸类化合物的水溶液中，超声分散0.5h后于50℃下将溶液蒸发完全，随后于40℃下真空干燥12h，将干燥后的材料放入管式炉中，在氮气保护下经高温热处理，获得Ni/N‑C复合材料。将本发明制备的Ni/N‑C电Fenton催化剂作为电Fenton阴极材料催化降解浓度为25mg·L‑1的罗丹明B溶液，5h内降解率达100％。
Description
一、技术领域
本发明涉及一种氮掺杂碳负载镍电Fenton催化剂的制备方法，是在碳材料表面原位修饰改性，得到氮掺杂碳负载镍复合材料，并将其作为电Fenton催化剂应用于有机废水降解处理。
二、背景技术
电Fenton催化氧化技术的原理是将溶解于水中的氧气在电解池的阴极还原产生H2O2，并在铁等催化剂的作用下分解生成氢自由基和羟基自由基氧化有机污染物，该技术的关键在于阴极材料的高催化活性。可用于电Fenton阴极的材料有石墨、碳-PTFE氧气扩散电极和三维电极如碳/石墨毡、活性碳纤维、玻璃态碳、海绵碳以及碳纳米管等。
碳/石墨毡由于具有较大的三维活性表面、结构完整、工业易得以及易于催化剂的负载与再生等优点而被广泛应用于处理废水中的有毒或难降解有机污染物，如染料、酚类、杀虫剂、药物以及垃圾渗透液等。目前为进一步提高电Fenton电极表面的催化活性，科研工作者在提高电极表面氧含量或比表面积等电化学活性方面开展了大量的研究，如热处理、酸处理(Shen et al.,Electrochim.Acta.2014,132,37-41；Miao et al.,Chem.Eng.J.2014,250,312-318)、化学和电化学氧化(Zhou et al.,Electrochim.Acta.2014,140,376-383)、有机改性(Wang et al.,CarbohydratePolymers,2011,86,1807-1813；Zhang et al.,Electrochim.Acta.,2008,53,5155-5161)金属或金属氧化物负载(Wang et al.,Appl.Catal.B:Environ.,2009,89,111-117；Li etal.,J.Hazard.Mater.,2009,164,18-25)，专利CN 103928689A报道了在常温空气阴极燃料电池阳极自发氧化亚铁离子，并通过热处理制备了具有不同电Fenton催化活性的FeOOH/C、Fe2O3/C、Fe3O4/C碳载纳米氧化铁复合材料。
三、发明内容
本发明旨在提供一种氮掺杂碳负载镍电Fenton催化剂的制备方法，首先采用浸渍法将镍离子与氨基羧酸类配体形成的配合物吸附到碳材表面，再通过热处理得到Ni/N-C复合材料。将该复合材料作为电Fenton阴极材料催化降解浓度为25mg·L-1的罗丹明B溶液，5h内使其降解率达100％，并保持较好的稳定性。
本发明氮掺杂碳负载镍电Fenton催化剂的制备方法，包括如下步骤：
将碳材前处理后放入马弗炉中，350℃下热处理1h，冷却后浸入镍盐和氨基羧酸类化合物的水溶液中，超声分散0.5h后于50℃下将溶液蒸发完全，随后于40℃下真空干燥12h，将干燥后的材料放入管式炉中，在氮气保护下经高温热处理，获得Ni/N-C复合材料。将本发明制备的Ni/N-C电Fenton催化剂作为电Fenton阴极材料催化降解浓度为25mg·L-1的罗丹明B溶液，5h内降解率达100％。
所述碳材选自碳纤维、碳毡或碳布。
所述碳材前处理的方法是先用1mol·L-1的盐酸浸泡0.5h，再用丙酮浸泡0.5h。
所述镍盐和氨基羧酸类化合物的水溶液中镍盐和氨基羧酸类化合物的摩尔比为1：1～6；所述镍盐选自硝酸镍、醋酸镍、氯化镍或硫酸镍；所述氨基羧酸类化合物为乙二胺四乙酸及其钠盐(EDTA)、氮川三乙酸(NTA)或二乙撑三胺五乙酸(DTPA)等中的一种；镍盐和氨基羧酸类化合物的水溶液中镍盐的量以镍单质的质量计占碳材质量的10～80％。
高温热处理过程中氮气的流速为30～100mL·s-1。
所述高温热处理是于500～900℃热处理0.5～3h。
本发明电Fenton催化降解实验是在一个双室电解池中进行，阴阳极室之间通过质子交换膜隔开，Ni/N-C复合材料为阴极，碳棒为阳极，0.05mol·L-1Na2SO4为电解质。将25mg·L-1的罗丹明B溶液加入到阴极室后，以30ml·s-1的流速从底部鼓入空气，并用导线将电池的阴阳极相连并接入2V直流源，每隔1h取样分析有机物降解率。5h内降解率达100％。
与已有技术相比，本发明的有益效果体现在：
1、本发明制备方法简单，易操作，周期短。
2、本发明采用氨基羧酸类化合物与镍盐配位，无需还原性气氛，通过一次热处理可形成镍氮共掺杂，起到协同催化作用。
3、本发明制备的Ni/N-C复合材料比表面积大，在应用于电Fenton催化反应时，能够快速吸附有机污染物并在电极附近实施快速降解，可应用于较高浓度有机污染物的降解，并且催化剂的可循环性良好。
四、附图说明
图1为实施例1制备的Ni/N-C复合材料的不同放大倍数SEM照片；
图2为实施例1制备的Ni/N-C复合材料的X射线衍射图；
图3为实施例1制备的Ni/N-C复合材料作为电Fenton阴极材料连续循环使用6次催化降解罗丹明B的浓度变化曲线图，其中罗丹明B的起始浓度为25mg·L-1，每次的降解时间为5h。
五、具体实施方式
以下结合部分技术方案详细叙述本发明的实施方式：
实施例1：
取面积为3×3cm2的碳毡0.6g，分别用1mol·L-1的盐酸和丙酮浸泡0.5h，随后将其放入马弗炉中350℃下热处理1h，冷却后浸入含有0.16mol·L-1硝酸镍和0.48mol·L-1EDTA的50mL水溶液中，超声分散0.5h后于50℃下缓慢将水分蒸法至有晶体析出时，取出材料并于40℃下真空干燥12h；将干燥后的材料放入管式炉中，在流速为80mL·s-1的氮气氛下，500℃热处理3h，获得Ni/N-C复合材料。
在一个容积均为250mL的双室电解池中，阴阳极室之间通过质子交换膜隔开，上述制备的Ni/N-C复合材料为阴极，直径为6mm、长4cm的碳棒为阳极，0.05mol·L-1Na2SO4为电解质。在电解池的阴极室加入25mg·L-1的罗丹明B溶液并以30ml·s-1的流速从底部鼓入空气，用导线将电池的阴阳极相连并接入2V直流源，接通电源后5h内罗丹明B的降解率达100％。
实施例2：
取面积为3×3cm2的碳毡0.6g，分别用1mol·L-1的盐酸和丙酮浸泡0.5h，随后将其放入马弗炉中350℃下热处理1h，冷却后浸入含有0.02mol·L-1醋酸镍和0.12mol·L-1NTA的50mL水溶液中，超声分散0.5h后于50℃下缓慢将水分蒸法至有晶体析出时，取出材料并于40℃下真空干燥12h；将干燥后的材料放入管式炉中，在流速为30mL·s-1的氮气氛下，700℃热处理2h后获得Ni/N-C复合材料。
在一个容积均为250mL的双室电解池中，阴阳极室之间通过质子交换膜隔开，上述制备的Ni/N-C复合材料为阴极，直径为6mm、长4cm的碳棒为阳极，0.05mol·L-1Na2SO4为电解质。在电解池的阴极室加入25mg·L-1的罗丹明B溶液并以30ml·s-1的流速从底部鼓入空气，用导线将电池的阴阳极相连并接入2V直流源，接通电源后4h内罗丹明B的降解率达100％。
实施例3：
取面积为3×3cm2的碳毡0.6g，分别用1mol·L-1的盐酸和丙酮浸泡0.5h，随后将其放入马弗炉中350℃下热处理1h，冷却后浸入含有0.05mol·L-1氯化镍和0.05mol·L-1DTPA的50mL水溶液中，超声分散0.5h后于50℃下缓慢将水分蒸法至有晶体析出时，取出材料并于40℃下真空干燥12h；将干燥后的材料放入管式炉中，在流速为100mL·s-1的氮气氛下，900℃热处理0.5h后得Ni/N-C复合材料。
在一个容积均为250mL的双室电解池中，阴阳极室之间通过质子交换膜隔开，上述制备的Ni/N-C复合材料为阴极，直径为6mm、长4cm的碳棒为阳极，0.05mol·L-1Na2SO4为电解质。在电解池的阴极室加入25mg·L-1的罗丹明B溶液并以30ml·s-1的流速从底部鼓入空气，用导线将电池的阴阳极相连并接入2V直流源，接通电源后4h内罗丹明B的降解率达100％。
Claims (7)
1.一种氮掺杂碳负载镍电Fenton催化剂的制备方法，其特征在于包括如下步骤：
将碳材前处理后放入马弗炉中，350℃下热处理1h，冷却后浸入镍盐和氨基羧酸类化合物的水溶液中，超声分散0.5h后于50℃下将溶液蒸发完全，随后于40℃下真空干燥12h，将干燥后的材料放入管式炉中，在氮气保护下经高温热处理，获得Ni/N-C复合材料。
2.根据权利要求1所述的制备方法，其特征在于：
所述碳材选自碳纤维、碳毡或碳布。
3.根据权利要求1所述的制备方法，其特征在于：
所述碳材前处理的方法是先用1mol·L-1的盐酸浸泡0.5h，再用丙酮浸泡0.5h。
4.根据权利要求1所述的制备方法，其特征在于：
所述镍盐和氨基羧酸类化合物的水溶液中镍盐和氨基羧酸类化合物的摩尔比为1：1～6；镍盐和氨基羧酸类化合物的水溶液中镍盐的量以镍单质的质量计占碳材质量的10～80％。
5.根据权利要求1或4所述的制备方法，其特征在于：
所述镍盐选自硝酸镍、醋酸镍、氯化镍或硫酸镍；所述氨基羧酸类化合物为乙二胺四乙酸及其钠盐、氮川三乙酸或二乙撑三胺五乙酸中的一种。
6.根据权利要求1所述的制备方法，其特征在于：
高温热处理过程中氮气的流速为30～100mL·s-1。
7.根据权利要求1所述的制备方法，其特征在于：
所述高温热处理是于500～900℃热处理0.5～3h。
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