CN112604704B - 一种珊瑚状磁性碳纳米复合材料及其制备方法和应用 - Google Patents
一种珊瑚状磁性碳纳米复合材料及其制备方法和应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- 238000000197 pyrolysis Methods 0.000 claims abstract description 15
- 229960002989 glutamic acid Drugs 0.000 claims abstract description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002253 acid Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 5
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
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- 238000004090 dissolution Methods 0.000 abstract description 2
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 18
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 4
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
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- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 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 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- AZLXCBPKSXFMET-UHFFFAOYSA-M sodium 4-[(4-sulfophenyl)diazenyl]naphthalen-1-olate Chemical compound [Na+].C12=CC=CC=C2C(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 AZLXCBPKSXFMET-UHFFFAOYSA-M 0.000 description 2
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- -1 iron ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
本发明提供一种珊瑚状磁性碳纳米复合材料及其制备方法和应用,属于污染水体修复技术领域。复合材料由多孔结构的石墨化碳纳米片堆积而成,具有珊瑚状形貌;石墨化碳纳米片含有氮基团,且内部嵌有铁氧化物纳米颗粒,有磁性;多孔的孔径为2~50nm;复合材料中铁与氮的摩尔比为(1~10):1,氮的质量分数为1%~12.5%。制备方法为二水柠檬酸钠在600~900℃煅烧1~3h后与铁盐、L‑谷氨酸加入酒精溶液中混合,蒸发酒精溶液后所得粉末在700~900℃热解2~6h。本发明通过一步热解将铁氧化物纳米颗粒包覆于石墨化碳纳米片中,同时掺杂氮杂原子,有效提高对水中有机污染物的去除能力,并降低金属溶出。
Description
技术领域
本发明属于污染水体修复技术领域,具体涉及一种珊瑚状磁性碳纳米复合材料及其制备方法和应用。
背景技术
随着工业化的快速发展,有机污染物造成的水体持续恶化,对人类健康和生态系统的可持续发展构成了巨大风险。有机污染物特别是抗生素和染料等持久性有机污染物,广泛存在于水体和土壤中,很难通过生物降解去除,传统的处理方法难于达到理想的去除效果。
近年来,先进的氧化过程(AOPs)被认为是一种在水生环境中原位分解不可生物降解的持久性有机污染物的高效手段。相较于传统的基于羟基自由基的高级氧化法,基于硫酸根自由基的高级氧化法(SR-AOPs)因其具有更高的氧化还原电位(2.5~3.1V)、更长的半衰期(30~40ms)及更宽的pH适用范围等优势,受到越来越多的关注。作为硫酸根自由基主要来源的过氧单硫酸盐,已经被证明可以被紫外、超声波、过渡金属、碳材料等有效激活。无金属的碳质材料因其优秀的生物相容性、出色的热稳定性和可调节的表面化学特性,在活化过氧单硫酸盐方面表现出优秀的潜力。然而,因为它们有限的活性位点和较低的电子转移效率,无金属的碳质催化剂的催化活性和长期耐受性仍然不能令人满意,从而阻碍了它的大规模应用。
最近,过渡金属-氮共掺杂碳材料,尤其是Fe-NC(铁氮共掺杂碳)的新型杂化催化剂似乎是过氧单硫酸盐活化的理想替代品。这是由于氮原子的掺入能够调整sp2杂化的碳骨架的电荷分布,并产生更多的点缺陷,另一方面,封装在碳壳中的金属可作为氧化还原过程中产生自由基的额外催化位点。但是,当前实现铁氮共掺杂的合成方法通常采用热解实现,反应过程中通过铁原子的迁移和团聚形成金属纳米颗粒,这一方法在酸性和强氧化环境中会有严重的金属浸出,导致催化剂失活严重和二次污染的问题。因此寻找一种具有大量活性位点,能快速有效去除水中有机污染物,且不存在金属浸出问题的催化剂是十分有意义的。
发明内容
针对现有技术的不足,以及本领域研究和应用的需求,本发明的目的在于提出了一种珊瑚状磁性碳纳米复合材料及其制备方法和应用,通过一步热解将铁氧化物纳米颗粒包覆于石墨化碳纳米片中,同时掺杂氮杂原子,可有效提高对水中有机污染物的去除能力,并降低金属溶出。
本发明的技术方案如下:
一种珊瑚状磁性碳纳米复合材料,其特征在于,所述复合材料由多孔结构的石墨化碳纳米片堆积而成,具有珊瑚状形貌;所述石墨化碳纳米片含有氮基团,且内部嵌有铁氧化物纳米颗粒;所述多孔的孔径为2~50nm;所述复合材料中铁与氮的摩尔比为(1~10):1,复合材料中氮的质量分数为1%~12.5%。
进一步地,所述复合材料的比表面积为10~700m2/g。
进一步地,所述氮基团包含吡啶型N、吡咯型N、NOx等。
进一步地,所述复合材料具有强磁性。
一种珊瑚状磁性碳纳米复合材料的制备方法,包括以下步骤:
步骤1、将二水柠檬酸钠干燥后研磨成粉末,然后在氮气下以2~10℃/min的升温速率升温至600~900℃煅烧1~3h,完成后,冷却至室温,研磨成粉末,经酸洗、洗涤至中性,干燥后得到粉末A;
步骤2、将步骤1所得粉末A与铁盐、L-谷氨酸加入无水乙醇和去离子水的体积比为1:(10~25)的酒精溶液中,充分搅拌,得到悬浊液;其中,悬浊液中L-谷氨酸的浓度为8mmol/L,粉末A与铁盐的质量比为1:(1~6),铁盐与L-谷氨酸的摩尔比为1:(1~10);
步骤3、真空蒸发步骤2所得悬浊液中的酒精溶液,完成后,经烘干、研磨后,得到粉末B;
步骤4、将步骤3所得粉末B置于管式炉内,在氮气或氩气氛围下,以2~5℃/min的升温速率升温至700~900℃热解2~6h,完成后,自然冷却至室温,经洗涤、干燥后,得到珊瑚状磁性碳纳米复合材料。
进一步地,步骤1干燥二水柠檬酸钠的条件为在100~200℃下干燥10~15h;步骤1所述酸洗采用的是0.5~2mol/L的盐酸、硝酸或硫酸。
进一步地,步骤2所述铁盐为FeCl3·6H2O、Fe2(SO4)3或Fe(NO3)3。
进一步地,步骤3中真空蒸发的步骤具体为真空旋转蒸发,蒸发温度为60~80℃,转速为100~120rmp/min。
进一步地,步骤4所述氮气或氩气的流量为50~100mL/min。
优选地,步骤1中干燥二水柠檬酸钠的条件为在155℃下中干燥12h;步骤4中的热解温度为800℃,时间2h。
本发明进一步提供了上述珊瑚状磁性碳纳米复合材料在催化降解水体中抗生素及有机染料的应用。
本发明的有益效果为:
1、本发明利用氨基酸中官能团与金属阳离子之间强烈的配位趋势,采用L-谷氨酸作为络合剂使铁离子均匀的分布在络合物中,并通过一步热解将铁元素掺杂入石墨化碳纳米片中,得到内嵌有铁氧化物纳米颗粒的石墨化碳纳米片,相比于现有技术,铁元素在官能团配位和石墨化碳包覆的共同作用下,极大地减少了金属溶出,降低二次污染所带来的环境风险;
2、本发明在一步热解掺入铁元素的同时将L-谷氨酸中的氮元素掺杂入石墨化碳纳米片中,掺杂的氮杂原子有助于提升电子转移效率,为石墨化碳纳米片增加更多的活性位点,提高对水中有机污染物的去除能力,同时具有优异的去除稳定性和重复性,拥有较高的经济价值;
3、本发明所述珊瑚状磁性碳纳米复合材料因铁元素的存在具有强磁性,解决了目前碳材料在水体中难以回收的问题;
4、本发明提供的珊瑚状磁性碳纳米复合材料的制备方法,操作简单,绿色环保,原料廉价易得,具有推广意义。
附图说明
图1为本发明实施例1所得珊瑚状磁性碳纳米复合材料(Fe,N@Cs-800)的SEM图;
图2为本发明实施例1所得珊瑚状磁性碳纳米复合材料(Fe,N@Cs-800)的BET测试数据图;其中,(a)为体积数据图,(b)为孔径数据图;
图3为本发明实施例1所得珊瑚状磁性碳纳米复合材料(Fe,N@Cs-800)和步骤1所得粉末A(Cs)的XRD图;
图4为本发明实施例1所得所得珊瑚状磁性碳纳米复合材料(Fe,N@Cs-800)的XPS图;其中,(a)为N1s分谱图,(b)为Fe2p分谱图;
图5为本发明实施例1~3所得珊瑚状磁性碳纳米复合材料和实施例1中步骤1所得材料首次去除盐酸四环素的效果图;
图6为本发明实施例1所得珊瑚状磁性碳纳米复合材料(Fe,N@Cs-800)分别对盐酸四环素、亚甲基蓝、罗丹明B和橙黄的催化降解效果图;
图7为本发明实施例1所得珊瑚状磁性碳纳米复合材料(Fe,N@Cs-800)重复使用去除盐酸四环素的效果图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
本实施例制备了一种珊瑚状磁性碳纳米复合材料(Fe,N@Cs-800),包括以下步骤:
步骤1、取25g的二水柠檬酸钠于烧杯中,在155℃的鼓风干燥箱中干燥12h,再研磨成粉末,转移至石英舟中,然后在氮气下以5℃/min的升温速率升温至800℃煅烧1h,完成后,自然冷却至室温,取出,研磨成粉末,经1mol/L的HCl溶液酸洗8h,去离子水洗涤至中性,干燥后得到粉末A;
步骤2、将步骤1所得0.16569g的粉末A与FeCl3·6H2O、L-谷氨酸加入由2mL无水乙醇和50mL去离子水组成的酒精溶液中,充分搅拌6h至混合均匀,得到悬浊液;其中,悬浊液中粉末A与FeCl3·6H2O的质量比为1:1,FeCl3·6H2O与L-谷氨酸的摩尔比为1:10;
步骤3、将步骤2所得悬浊液在温度为80℃、转速为105rmp/min下真空旋转蒸发掉酒精溶液,完成后,经80℃烘干、研磨后,得到粉末B;
步骤4、将步骤3所得粉末B转移至刚玉舟中,置于管式炉内,在流量为100mL/min的氮气保护下,以2℃/min的升温速率升温至800℃热解2h,完成后,自然冷却至室温,取出,经1mol/L的HCl溶液酸洗8h,去离子水洗涤至中性,抽滤,然后80℃下真空烘干,得到珊瑚状磁性碳纳米复合材料(Fe,N@Cs-800)。
对所得Fe,N@Cs-800进行SEM测试,测试图如图1所示,可以看出所得Fe,N@Cs-800由碳纳米片堆积而成,具有珊瑚状形貌。
根据如图2所示的BET测试结果,可知所得Fe,N@Cs-800的孔容为0.219m3/g,并且孔径全部分布于2~50nm,属于介孔碳,由BJH测试法得到比表面积为74.07m2/g,。
根据如图3所示的Fe,N@Cs-800和步骤1所得粉末A(Cs)的XRD图,可知所得Fe,N@Cs-800和粉末A在2θ=26.2°和44.3°处出现了两个宽峰,分别对应于石墨碳的(002)和(101)晶面,说明所制得Fe,N@Cs-800和Cs材料均具有较高的石墨化程度。
根据如图4所示的XPS图,由图4(a)可知所得Fe,N@Cs-800的N1s分谱图在398.4eV、399.7eV、400.8eV和404.8eV处出现了特征峰,分别对应为吡啶型N、吡咯型N、Fe-Nx和NOx,表明了氮元素的成功掺入;并图4(b)可知所得Fe,N@Cs-800在710~735eV的范围内解卷积,其中每个峰代表一种氧化态为Fe2+或Fe3+的铁。在718eV附近出现的卫星峰也表明了铁氧化物出现。综上所诉,Fe元素成功地掺入碳纳米材料中,且存在有铁氧化物。
对本实施例所得Fe,N@Cs-800进行水中抗生素(盐酸四环素)和有机染料的催化降解性能测试,具体步骤如下:
(1)将盐酸四环素、亚甲基蓝、橙黄Ι、亚甲基蓝分别准确配置50mL、20mg/L的溶液,不调节pH值,直接转入100mL锥形瓶中;
(2)准确称取10mg所得Fe,N@Cs-800和0.0154g过氧单硫酸钾盐(PMS)加入锥形瓶中,将锥形瓶放入恒温振荡器中,200rpm、25℃下振荡,一定的时间间隔取样测试浓度。
由图5所示首次去除盐酸四环素的效果图可以看出,本实施例所得Fe,N@Cs-800具有优异的去除抗生素的能力,通过吸附和催化降解的方法,在12min可以达到91%左右的盐酸四环素去除率;并且通过与Cs首次去除盐酸四环素的效果对比,可看出在石墨化碳中掺入铁和氮元素能有效提升盐酸四环素去除率;
再根据图6所示对不同典型污染物(盐酸四环素、亚甲基蓝、罗丹明B、橙黄Ⅰ)的催化降解效果图,可知在15min内95%以上的有机染料能被降解,盐酸四环素也能达到90%左右的去除率;图7为重复使用Fe,N@Cs-800去除盐酸四环素的效果图,可知本实施例所得Fe,N@Cs-800经过四次循环后,通过吸附和催化降解的方法,抗生素的去除率仍达到第一次使用时的70%,表明在去除盐酸四环素过程中,Fe,N@Cs-800具有较好的稳定性和重复使用性,具有较好的经济效益。
实施例2
本实施例制备了一种珊瑚状磁性碳纳米复合材料(Fe,N@Cs-700),制备方法与实施例1相比,区别仅在于步骤4中将升温至800℃热解2h调整为升温至700℃热解2h,即在流量为100mL/min的氮气保护下,以2℃/min的升温速率升温至700℃热解2h;其他步骤不变。实验表明,所得Fe,N@Cs-700的比表面积为80.32m2/g,孔容为0.249cm3/g,平均孔径在2~50nm内。
对本实施例所得Fe,N@Cs-700采用与实施例1相同的方法进行盐酸四环素的去除性能测试,由图5所示首次去除盐酸四环素的效果图可以看出,本实施例所得Fe,N@Cs-700通过吸附和催化降解的方法,在12min可以达到82%左右的去除率。
实施例3
本实施例制备了一种珊瑚状磁性碳纳米复合材料(Fe,N@Cs-900),制备方法与实施例1相比,区别仅在于步骤4中将升温至800℃热解2h调整为升温至900℃热解2h,即在流量为100mL/min的氮气保护下,以2℃/min的升温速率升温至900℃热解2h;其他步骤不变。实验表明,所得Fe,N@Cs-900的比表面积为71.99m2/g,孔容为0.222cm3/g,平均孔径在2~50nm内。
对本实施例所得Fe,N@Cs-900采用与实施例1相同的方法进行盐酸四环素的去除性能测试,由图5所示首次去除盐酸四环素的效果图可以看出,本实施例所得Fe,N@Cs-900通过吸附和催化降解的方法,在12min可以达到84%左右的去除率。
对比例1
本对比例制备了一种不掺杂氮的磁性碳纳米复合材料(Fe@Cs-800),制备方法与实施例1相比,区别仅在于步骤2中不加入L-谷氨酸,即粉末A只与FeCl3·6H2O加入由2mL无水乙醇和50mL去离子水组成的酒精溶液中;其他步骤不变。
对比例2
本对比例制备了一种不掺杂铁的碳纳米复合材料(N@Cs-800),制备方法与实施例1相比,区别仅在于步骤2中不加入FeCl3·6H2O,即粉末A只与L-谷氨酸加入由2mL无水乙醇和50mL去离子水组成的酒精溶液中;其他步骤不变。
根据图5所示首次去除盐酸四环素的效果图可以看出,对比例1、2所得材料的去除效果均不如实施例1所得Fe,N@Cs-800,表明在石墨化碳纳米片中掺入铁元素和氮元素,对于提升其去除性能均有明显效果。
综上所述,采用本发明所述方法制得的珊瑚状磁性碳纳米复合材料具有很强的活化过氧单硫酸盐能力,进而能够快速高效地在去除水中抗生素和有机染料;铁氧化物被包覆于碳纳米材料中,能有效避免金属的溶出,同时具有较好的稳定性,拥有较高的经济价值;氮杂原子的掺入使得碳纳米材料产生更多的缺陷结构,拥有更多的活性点位。
Claims (5)
1.一种用于催化降解水中抗生素和有机染料的珊瑚状磁性碳纳米复合材料的制备方法,其特征在于,包括以下步骤:
步骤1、将二水柠檬酸钠干燥后,研磨成粉末,再在氮气下以2~10 ℃/min的升温速率升温至600~900 ℃煅烧1~3 h,完成后,冷却至室温,研磨成粉末,经酸洗、洗涤至中性,干燥后得到粉末A;
步骤2、将步骤1所得粉末A与铁盐、L-谷氨酸加入酒精溶液中,搅拌后得到悬浊液;其中,悬浊液中L-谷氨酸的浓度为8 mmol/L,粉末A与铁盐的质量比为1:(1~6),铁盐与L-谷氨酸的摩尔比为1:(1~10);
步骤3、真空蒸发步骤2所得悬浊液中的酒精溶液,完成后,经烘干、研磨后,得到粉末B;
步骤4、将步骤3所得粉末B置于管式炉内,在氮气或氩气氛围下,以2~5 ℃/min的升温速率升温至700~900 ℃热解2~6 h,完成后,冷却至室温,经洗涤、干燥后,得到珊瑚状磁性碳纳米复合材料;所述珊瑚状磁性碳纳米复合材料由多孔结构的石墨化碳纳米片堆积而成,具有珊瑚状形貌;所述石墨化碳纳米片含有氮基团,且内部嵌有铁氧化物纳米颗粒;所述多孔的孔径为2~50 nm;所述复合材料中铁与氮的摩尔比为(1~10):1,氮的质量分数为1%~12.5%。
2.根据权利要求1所述用于催化降解水中抗生素和有机染料的珊瑚状磁性碳纳米复合材料的制备方法,其特征在于,步骤2所述铁盐为FeCl3·6H2O、Fe2(SO4)3或Fe(NO3)3。
3.根据权利要求1所述用于催化降解水中抗生素和有机染料的珊瑚状磁性碳纳米复合材料的制备方法,其特征在于,步骤2所述酒精溶液中无水乙醇和去离子水的体积比为1:(10~25)。
4. 根据权利要求1所述用于催化降解水中抗生素和有机染料的珊瑚状磁性碳纳米复合材料的制备方法,其特征在于,步骤1所述酸洗采用的是0.5~2 mol/L的盐酸、硝酸或硫酸。
5. 根据权利要求1所述用于催化降解水中抗生素和有机染料的珊瑚状磁性碳纳米复合材料的制备方法,其特征在于,步骤3中真空蒸发的步骤具体为真空旋转蒸发,蒸发温度为60~80 ℃,转速为100~120 rmp/min。
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