CN114713259B - 钴碳氮中空多面体催化剂的制备及其在降解新兴污染物中的应用 - Google Patents
钴碳氮中空多面体催化剂的制备及其在降解新兴污染物中的应用 Download PDFInfo
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Abstract
本发明属于新兴污染物处理技术领域,具体涉及钴碳氮中空多面体催化剂的制备及其在降解新兴污染物中的应用。本发明利用新型的MOF材料合成方法制备得到钴碳氮中空多面体新型催化剂,该催化剂能激活过硫酸盐,从而降解水体中的PPCPs污染物,相较于传统金属盐类催化材料的激活体系,本发明利用了新型MOF材料的合成方法,可以在减少钴金属溶出的同时,高效降解PPCPs,甚至对低浓度(ppb级别)PPCPs也有较好的降解效果,且适用的PH范围广。
Description
技术领域
本发明属于新兴污染物处理技术领域,具体涉及钴碳氮中空多面体催化剂的制备及其在降解新兴污染物中的应用。
背景技术
新兴污染物contaminants of emerging concern(CECs)特指那些可能对人体健康或者生态系统产生影响、但目前尚未(或者最近才)被管控的化学物质,主要包括药品与个人护理用品(Pharmaceuticals and Personal Care Products,简称PPCPs)、持久性有机污染物(Persistent Organic Pollutants,简称POPs)、消毒副产物(Disinfection By-products,简称DBPs)、汞等以及它们的降解产物。其中,最常见的PPCPs包括人类和兽用药物,如消炎药、止痛药、抗生素、β-受体阻滞剂、抗抑郁药、血脂调节剂,以及个人护理品中的消毒剂或芳香剂等。虽然PPCPs在环境中的浓度一般在ng/L到μg/L之间,但其具有一定的极性、且难以挥发,会在水环境中不断积累,从而影响藻类、水生生物的生理活动,严重破坏生态系统的平衡。
高级氧化技术能产生具有一定氧化能力的自由基物种,因而能高效降解PPCPs,主要包括芬顿氧化技术和光催化氧化技术。其中,芬顿氧化技术的核心在于使用不同的金属基催化剂分解双氧水产生羟基自由基,但其均相催化受限于金属物质的溶解度,且对于某些具有高可溶性的金属物种而言,由于具有细胞毒性特性而使其应用受到限制,此外,多相催化剂的不稳定以及无法循环利用也成为限制其推广应用的另一重要因素。而光催化氧化技术则是利用光能产生光生电子空穴对来降解PPCPs,其不仅可以去除化学上稳定且不可生物降解的有机污染物,而且可以在温和的条件下有效降解痕量有机污染物,且产生的副产物较少,相比而言具有更明显的优势。但紫外、热、超声、电化学等光催化氧化条件均需要额外借助能量才能激活过氧化物来产生自由基,而金属氧化物在激活过硫酸盐后可能会导致水体金属溶出量过高,污染水体。因此,需要开发具有足够催化活性,制备方便,且使用后对环境友好的新型催化剂。
发明内容
为了克服上述现有技术的不足,本发明的首要目的是提供一种钴碳氮中空多面体催化剂的制备方法。
本发明的第二个目的是提供采用上述制备方法制备得到的钴碳氮中空多面体催化剂在降解新兴污染物中的应用。
本发明的上述第一个目的是通过以下技术方案来实现的:
本发明提供一种钴碳氮中空多面体催化剂的制备方法,具体为:首先分别将钴盐和2-甲基咪唑溶解在有机溶液中制备得溶液A和溶液B,然后将溶液A倒入溶液B中,经老化后分离收集产物,产物经洗涤和干燥后得到Co-MOF,Co-MOF再于H2和Ar的混合气体氛围下煅烧后制备得到钴碳氮中空多面体催化剂。
优选地,所述钴盐包括Co(NO3)2·6H2O。
优选地,所述钴盐在溶液A中的浓度为(0.7-1.0)g/75mL,所述2-甲基咪唑在溶液B中的浓度(0.8-1.1)g/75mL,所述溶液A和溶液B的体积比为1:1。进一步地,所述钴盐在溶液A中的浓度为0.873g/75mL,所述2-甲基咪唑在溶液B中的浓度0.984g/75mL。
优选地,将溶液A倒入溶液B中时,需在剧烈搅拌下将溶液A快速倒入溶液B中。
优选地,老化的时间为12-36h。进一步地,老化的时间为24h。
优选地,H2和Ar的体积比为(1-2):(8-9)。进一步地,H2和Ar的体积比为1:9。
优选地,煅烧的温度为(700-900)℃,时间为(1-3)h,升温速度为(4-6)℃/min。进一步地,煅烧的温度为800℃,时间为2h,升温速度为5℃/min。
本发明的上述第二个目的是通过以下技术方案来实现的:
本发明还提供了采用上述的制备方法制备得到的钴碳氮中空多面体催化剂。
本发明还提供了采用上述的钴碳氮中空多面体催化剂在降解新兴污染物中的应用。
优选地,所述新兴污染物为PPCPs。
本发明利用新型的MOF材料合成方法制备得到一种钴碳氮中空多面体新型催化剂,并探究了其在高浓度(ppm级别)和低浓度(ppb级别)中对PPCPs的降解差异,经研究发现,该催化剂能激活过硫酸盐,从而降解水体中的PPCPs污染物,并能运用于实际水体,相较于传统的金属盐类催化材料激活体系,既降低了金属的溶出,又能在减少金属溶出的同时高效降解PPCPs,且适用的PH范围广。
进一步地,所述PPCPs包括双氯芬酸钠、萘普生、环丙沙星、恩诺沙星、卡马西平、氧氟沙星和布诺芬。
本发明还提供了一种降解新兴污染物的方法,即往受新兴污染物污染的水体中投入上述的钴碳氮中空多面体催化剂和的过硫酸盐。
优选地,所述钴碳氮中空多面体催化剂的投放量为0.2mg/L,过硫酸盐的投放量为0.5μmol/L。
与现有技术相比,本发明的有益效果是:
本发明公开了一种钴碳氮中空多面体催化剂的制备方法,利用新型的MOF材料合成方法制备得到钴碳氮中空多面体新型催化剂,该催化剂能激活过硫酸盐,从而降解水体中的PPCPs污染物,相较于传统金属盐类催化材料的激活体系,本发明利用了新型MOF材料的合成方法,可以在减少钴金属溶出的同时,高效降解PPCPs,甚至对低浓度(ppb级别)PPCPs也有较好的降解效果,且适用的PH范围广。
附图说明
图1为钴碳氮中空多面体的SEM图;
图2为钴碳氮中空多面体的XPS谱图(碳钴波峰);
图3为五次循环的金属钴溶出量情况;
图4为钴碳氮中空多面体对五种不同水样中的DCF的降解效果(C为降解后的DCF浓度,C0为DCF的初始浓度);
图5为钴碳氮中空多面体对PPCPs混合污染物的降解效果(C为降解后的DCF浓度,C0为DCF的初始浓度);
图6为钴碳氮中空多面体对不同pH水样中的DCF的降解效果(C为降解后的DCF浓度,C0为DCF的初始浓度);
图7为钴碳氮中空多面体对高浓度(ppm级别)DCF的降解效果(C为降解后的DCF浓度,C0为DCF的初始浓度)。
具体实施方式
下面对本发明的具体实施方式作进一步说明。在此需要说明的是,对于这些实施方式的说明用于帮助理解本发明,但并不构成对本发明的限定。此外,下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
下述实施例中的实验方法,如无特殊说明,均为常规方法,下述实施例中所用的试验材料,如无特殊说明,均为可通过常规的商业途径购买得到。
实施例1钴碳氮中空多面体催化剂的制备
将0.873g Co(NO3)2·6H2O溶解在75mL甲醇溶液中得到溶液A;并将0.984g 2-甲基咪唑溶解在75mL甲醇溶液中得到溶液B,然后在500rpm搅拌下将溶液A快速倒入溶液B中,搅拌1min后将混合液静置老化24h,得到的紫色产物通过离心分离并用甲醇清洗四次,再于70℃下干燥过夜得到ZIF-67粉末(Co-MOF),最后将ZIF-67粉末置于10%H2/Ar的混合气体(即10%H2、90%Ar)氛围下以5℃/min的升温速度升温至800℃,并在800℃下煅烧2小时,得到钴碳氮中空多面体催化剂。
对制备所得的钴碳氮中空多面体进行扫描电子显微镜(SEM)测试。从图1的高分辨率微区形貌分析可以看到,该钴碳氮材料为中空多面立方体的形状,这种形状能够大大增加钴碳氮催化剂激活过硫酸盐的活性位点。
对制备所得的钴碳氮中空多面体进行x射线光电子能谱(XPS)分析。由图2可以看出,该钴碳氮材料上存在碳和钴的化学键,是一种钴碳合成的新型催化剂。
实施例2钴碳氮中空多面体催化剂的制备
将0.70g Co(NO3)2·6H2O溶解在75mL甲醇溶液中得到溶液A;并将0.80g 2-甲基咪唑溶解在75mL甲醇溶液中得到溶液B,然后在剧烈搅拌下将溶液A快速倒入溶液B中,搅拌1min后将混合液静置老化12h,得到的紫色产物通过离心分离并用甲醇清洗数次,再于70℃下干燥过夜得到ZIF-67粉末(Co-MOF),最后将ZIF-67粉末置于15%H2/Ar的混合气体(即15%H2、85%Ar)氛围下以4℃/min的升温速度升温至700℃,并在700℃下煅烧3小时,得到钴碳氮中空多面体催化剂。
实施例3钴碳氮中空多面体催化剂的制备
将1.00g Co(NO3)2·6H2O溶解在75mL甲醇溶液中得到溶液A;并将1.10g 2-甲基咪唑溶解在75mL甲醇溶液中得到溶液B,然后在剧烈搅拌下将溶液A快速倒入溶液B中,搅拌1min后将混合液静置老化36h,得到的紫色产物通过离心分离并用甲醇清洗数次,再于70℃下干燥过夜得到ZIF-67粉末(Co-MOF),最后将ZIF-67粉末置于20%H2/Ar的混合气体(即20%H2、80%Ar)氛围下以6℃/min的升温速度升温至900℃,并在900℃下煅烧1小时,得到钴碳氮中空多面体催化剂。
实验例1钴碳氮中空多面体催化剂的性能测试
(1)钴浸出量实验
将实施例1制备所得的钴碳氮中空多面体催化剂投入到试验用水中,然后使用ICP-OES电感耦合等离子体发射光谱仪测量五次循环的钴浸出量。
由图3可以看出,该钴碳氮催化剂的金属钴溶出量低,在激活过硫酸盐循环降解污染物PPCPs的过程中,其金属钴的溶出量低于环境容许值的标准(1mg/L),说明该催化剂对环境友好,且很有应用前景。
(2)对不同水样中DCF的降解效果
五种水样(海水,污水,井水,自来水,试验用水,其中海水和井水从广东惠州获取,污水来源于佛山镇安污水处理厂,自来水为日常生活用水,实验用水由超纯水机获取),各取100mL,各水样中的PPCPs均为双氯芬酸(DCF),DCF的浓度为30ppb(30μg/L),然后加入0.2mg/L实施例1制备的钴碳氮中空多面体催化剂和0.5μmol/L的过硫酸盐,最后通过高效液相色谱仪(lc-ms)测量DCF的浓度变化(每两分钟测一次),以观察钴碳氮中空多面体催化剂激活过硫酸盐产生羟基自由基和硫酸根自由基来高效降解水中PPCPs污染物的情况。
由图4可以看出,该钴碳氮中空多面体催化剂能激活过硫酸盐降解不同水体中的双氯芬酸钠(ppb级别),而且基本都能在10分钟内完全降解。
(3)对混合污染物(PPCPs)的降解效果
取100mL超纯水,并加入PPCPs混合污染物【双氯芬酸钠(DCF)、萘普生(NPX)、环丙沙星(CIP)、恩诺沙星(ENR)、卡马西平(CBZ)、氧氟沙星(OFX)、布诺芬(IBU),各污染物的浓度均为50ppb】,然后再加入0.2mg/L实施例1制备的钴碳氮中空多面体催化剂,0.5μmol/L的过硫酸盐,最后通过高效液相色谱仪(lc-ms)测量各PPCPs污染物的浓度变化(每两分钟测一次),以观察钴碳氮中空多面体催化剂激活过硫酸盐产生羟基自由基和硫酸根自由基来高效降解水中污染物的情况。
由图5可以看出,该钴碳氮中空多面体催化剂具有较好的混合污染物降解效果,大多数污染物在10分钟内都能降解60%以上,快速高效,说明该催化剂具有很好的应用前景。
(4)在不同pH水样中对DCF的降解效果
五种不同pH试验用水(pH分别为3、5、7、9、11)各取100mL,各试验用水均含30ppb(30μg/L)的DCF,然后加入0.2mg/L实施例1制备的钴碳氮中空多面体催化剂和0.5μmol/L的过硫酸盐,最后通过高效液相色谱仪(lc-ms)测量DCF的浓度变化(每两分钟测一次),以观察钴碳氮中空多面体催化剂激活过硫酸盐产生羟基自由基和硫酸根自由基来高效降解水中PPCPs污染物的情况。
由图6可以看出,在3-11的pH范围内,该钴碳氮中空多面体催化剂对DCF的降解效果差距不大,说明该钴碳氮中空多面体催化剂的适用PH范围广。
(5)对高浓度(ppm级别)DCF的降解效果
五种不同ppm级别的试验用水(含DCF的浓度分别为10、20、30、40、50ppm)各取100mL,然后加入0.2mg/L实施例1制备的钴碳氮中空多面体催化剂和0.5μmol/L的过硫酸盐,最后通过高效液相色谱仪(lc-ms)测量DCF的浓度变化(每一分钟测一次),以观察钴碳氮中空多面体催化剂激活过硫酸盐产生羟基自由基和硫酸根自由基来高效降解水中PPCPs污染物的情况。
由图7可以看出,在10-50ppm的DCF浓度范围内,该钴碳氮中空多面体催化剂在5分钟内即可降解70%以上的DCF,说明该钴碳氮中空多面体催化剂对高浓度(ppm级别)PPCPs污染物具有较好的降解效果。
以上对本发明的实施方式作了详细说明,但本发明不限于所描述的实施方式。对于本领域的技术人员而言,在不脱离本发明原理和精神的情况下,对这些实施方式进行多种变化、修改、替换和变型,仍落入本发明的保护范围内。
Claims (1)
1.一种钴碳氮中空多面体催化剂在降解新兴污染物双氯芬酸钠中的应用,其特征在于,所述钴碳氮中空多面体催化剂的制备方法为:首先分别将Co(NO3)2·6H2O和2-甲基咪唑溶解在甲醇溶液中制备得溶液A和溶液B,然后将溶液A倒入溶液B中,所述Co(NO3)2·6H2O在溶液A中的浓度为(0.7-1.0)g/75mL,所述2-甲基咪唑在溶液B中的浓度(0.8-1.1)g/75mL,所述溶液A和溶液B的体积比为1:1,经老化后分离收集产物,产物经洗涤和干燥后得到Co-MOF,Co-MOF再于H2和Ar的混合气体氛围下煅烧后制备得到钴碳氮中空多面体催化剂,H2和Ar的体积比为(1-2):(8-9),煅烧的温度为(700-900)℃,时间为(1-3)h,升温速度为(4-6)℃/min;所述钴碳氮中空多面体催化剂通过激活过硫酸盐降解水体中的双氯芬酸钠。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108525635A (zh) * | 2018-04-24 | 2018-09-14 | 福州大学 | 一种基于mof的磁性氮掺杂碳纳米管的制备方法及其应用 |
CN110479224A (zh) * | 2019-07-31 | 2019-11-22 | 同济大学 | 一种有机金属框架衍生的钴/氮碳纳米材料及其制备方法和应用 |
CN112169822A (zh) * | 2020-10-21 | 2021-01-05 | 南京大学 | 高效活化过硫酸盐的氮掺杂中空碳多面体@碳纳米管基单原子钴催化剂及其制备方法 |
CN112958092A (zh) * | 2021-02-05 | 2021-06-15 | 暨南大学 | 一种活化过硫酸盐催化剂及其制备方法与应用 |
CN113000062A (zh) * | 2021-03-04 | 2021-06-22 | 辽宁大学 | 氮掺杂碳材料及其制备方法和应用 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108525635A (zh) * | 2018-04-24 | 2018-09-14 | 福州大学 | 一种基于mof的磁性氮掺杂碳纳米管的制备方法及其应用 |
CN110479224A (zh) * | 2019-07-31 | 2019-11-22 | 同济大学 | 一种有机金属框架衍生的钴/氮碳纳米材料及其制备方法和应用 |
CN112169822A (zh) * | 2020-10-21 | 2021-01-05 | 南京大学 | 高效活化过硫酸盐的氮掺杂中空碳多面体@碳纳米管基单原子钴催化剂及其制备方法 |
CN112958092A (zh) * | 2021-02-05 | 2021-06-15 | 暨南大学 | 一种活化过硫酸盐催化剂及其制备方法与应用 |
CN113000062A (zh) * | 2021-03-04 | 2021-06-22 | 辽宁大学 | 氮掺杂碳材料及其制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
Persulfate activation by ZIF-67-derived cobalt/nitrogen-doped carbon composites: Kinetics and mechanisms dependent on persulfate precursor;Yudong Xue, et al;Chemical Engineering Journal;第408卷;文章第127305(2)页第2节,第127305(3)页3.1节,第127305(4)页Fig.1、Fig.2,第127305(6)页Fig.4 * |
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