CN113181918A - 非金属矿物诱导双单原子催化剂及其制备和应用 - Google Patents
非金属矿物诱导双单原子催化剂及其制备和应用 Download PDFInfo
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- CN113181918A CN113181918A CN202110443139.3A CN202110443139A CN113181918A CN 113181918 A CN113181918 A CN 113181918A CN 202110443139 A CN202110443139 A CN 202110443139A CN 113181918 A CN113181918 A CN 113181918A
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- Prior art keywords
- catalyst
- preparing
- double
- acid
- nonmetallic minerals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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Abstract
本发明公开了一种非金属矿物诱导制备双单原子催化剂的方法,包括以下步骤:将天然非金属矿物均匀分散于水中,充分搅拌得到浆料;向浆料中加入过渡金属盐和碳源,调节pH值至7‑10,充分搅拌反应后,过滤,洗涤,干燥,得到固体混合物;将固体混合物进行焙烧处理,得焙烧产物;将焙烧产物,进行酸洗,水洗至pH为中性,干燥后,得MSi双单原子催化剂。本发明所得催化剂中过渡金属与硅以双单原子形式共同存在,保留了天然非金属矿物的微观形貌与多孔结构,并在活化过硫酸盐体系中,具有降解污染物效率高、稳定性好、重复使用性能优异、适用范围广、重金属离子二次污染风险低的有益效果。
Description
技术领域
本发明涉及催化剂领域。更具体地说,本发明涉及一种非金属矿物诱导双单原子催化剂及其制备和应用。
背景技术
随着工业的发展和社会的进步,环境污染的控制与治理成为各国日益关注的焦点问题。其中,内分泌干扰物、抗生素、毒素、农药、持久性有机污染物、染料等有机污染物,随污水排放或渗透进入生活用水系统,严重威胁人类的生命安全。
目前,工业中有机废水处理的常用方法主要为物理吸附、微生物降解、膜过滤、化学氧化等,仍存在处理效率低、受天然水体中非金属离子与天然有机质(NOM)影响较大、运行成本较高、耗材二次处理成本高等不足。
近年来,基于硫酸根自由基的新兴高级氧化体系因其强氧化能力、高选择性、适用范围广等优点,在有机污染水体的修复领域展现了良好的应用前景。硫酸根自由基可通过活化过硫酸盐产生。其中,紫外活化、微波活化、热活化及碱活化工艺复杂;石墨烯、氮掺杂石墨烯等碳基材料活化效率较低,成本较高;而过渡金属离子(Co2+、Fe2+、Mn2+、Ni2+、Ag+等)活化中的重金属离子残留会对水环境产生二次污染。尽管过渡金属氧化物(单金属氧化物(Co3O4、Fe2O3、MnO2等)或多金属氧化物(FeCo2O4、CuFe2O4、FeNi2O4等))可以从一定程度上缓解上述过硫酸盐活化工艺中存在的问题,但仍然面临活化效率相对较低、重金属离子析出、催化材料回收困难等问题,难以满足污水处理厂的工艺需求。因此,迫切需求开发设计一种超高效、低成本、环境友好的异相催化剂,用于推动基于硫酸根自由基的新兴高级氧化体系的广泛应用。
发明内容
本发明为解决现有催化剂在活化过硫酸盐降解有机物体系中活化速率低、过渡金属离子析出、回收困难、成本高等问题,提供了一种具有高效、安全、低成本、易回收、适用范围广等优越性能的用于过硫酸盐活化的催化剂的制备方法,及利用其活化过硫酸盐降解有机污染物的方法。
为了实现根据本发明的这些目的和其它优点,提供了一种非金属矿物诱导双单原子催化剂的制备方法,包括以下步骤:
步骤1、将天然非金属矿物均匀分散于水中,充分搅拌得到浆料,所述浆料中天然非金属矿物的浓度为40-90g/L;
步骤2、向步骤1所得的浆料中加入过渡金属盐和碳源,调节pH值至7-10,充分搅拌反应后,过滤、洗涤、干燥,得到固体混合物,所述过渡金属用量为0.86-1.73g/L,所述碳源用量为4-10g/L;
步骤3、将步骤2所得的固体混合物,进行焙烧处理,得焙烧产物;
步骤4、将步骤3所得的焙烧产物,进行酸洗,水洗至pH为中性,干燥后,得MSi双单原子催化剂,其中,M代表Co、Mn、Cu、Ni、Fe中的一种。
优选的是,所述天然非金属矿物是膨润土、高岭石、硅藻土、蛭石、凹凸棒、海泡石、埃洛石、粉石英、沸石中的一种或两种。
优选的是,所述过渡金属盐为钴盐、锰盐、镍盐、铜盐、铁盐中的一种;所述过渡金属盐的阴离子为硫酸根离子、氯离子、硝酸根离子、乙酸根离子中的一种。
优选的是,所述碳源为苯胺、盐酸多巴胺、吡咯、吡啶中的一种或两种。
优选的是,步骤2中,调节pH的调节剂为盐酸、硫酸、磷酸、氢氧化钠、磷酸二氢钠、Tris-buffer中的一种或多种。
优选的是,步骤2中,所述干燥温度为40-80℃、时间为4-12h.。
优选的是,步骤3中,所述焙烧处理温度为600-1000℃、时间为0.5-4h、升温速率为4-8℃/min;所述焙烧气氛为氩气、氮气、空气、氦气中的一种或两种。
优选的是,步骤4中,所述酸洗中酸为硫酸、盐酸、氢氟酸、硝酸中的一种,所述酸的质量分数为5%-20%,所述酸洗时间为1-48h,所述干燥温度为40-80℃、时间为4-12h。
本发明提供一种双单原子催化剂,由所述的非金属矿物诱导制备双单原子催化剂的方法制备而得。
本发明提供一种双单原子催化剂在活化过硫酸盐降解有机污染物中的应用,向待处理有机污染物中投加MSi双单原子催化剂及过硫酸盐,以去除有机污染物,所述过硫酸盐为过一硫酸钾、过硫酸钠、过硫酸铵、过二硫酸钾、过二硫酸钠、过硫酸铵中的一种或多种。
本发明至少包括以下有益效果:
(1)本发明采用储量丰富、价格低廉的天然非金属矿物为原料,诱导制备MSi双单原子催化剂,降低了催化剂的制备成本;
(2)本发明提供的MSi双单原子催化剂比表面积高达480m2/g,孔结构丰富,且亲水性能优异;
(3)本发明提供的MSi双单原子催化剂为固体粉末,便于携带和运输;此外,MSi双单原子催化剂直径大于20μm,可通过快速沉降进行回收;
(4)本发明提供的MSi双单原子催化剂活化过硫酸盐降解污染物效率高,显著降低催化剂及过硫酸盐的消耗量;MSi双单原子催化剂活化过硫酸盐使用稳定性好,重复使用性能优异,适用范围广;
(5)本发明提供的MSi双单原子催化剂中过渡金属含量低于0.1%,活化过硫酸盐降解污染物后,水中过渡金属离子残余低于0.1μg/L,显著降低重金属离子二次污染风险。
本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明
图1为本发明实施1中制备的CoSi双单原子催化剂的球差电镜及相应元素面扫图;
图2为本发明实施1中制备的CoSi双单原子催化剂的X射线衍射图谱;
图3为本发明实施例1和对比例1中制备的催化剂在活化过硫酸盐降解双酚A废水中的应用对比研究效果图;
图4为本发明实施例1的CoSi双单原子催化剂在催化降解双酚A废水、阿特拉津废水、罗丹明B废水、四环素废水的降解效果图;
图5为本发明不同质量的实施例1的CoSi双单原子催化剂降解双酚A废水的降解效果图;
图6为本发明不同过一硫酸钾用量对于实施例1的CoSi双单原子催化剂在活化过硫酸盐降解双酚A废水中的影响研究效果图;
图7为本发明不同反应pH值对于实施例1的CoSi双单原子催化剂在活化过硫酸盐降解双酚A废水的影响研究效果图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。
需要说明的是,下述实施方案中所述实验方法,如无特殊说明,均为常规方法,所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1:
本实施例制备CoSi双单原子催化剂。
将90g硅藻土均匀分散于1L水中,充分搅拌后,加入1.08g乙酸钴及10g盐酸多巴胺,并采用Tris-buffer调节pH值至8.5;反应8h后,过滤,洗涤,并在60℃下干燥8h,得到固体混合物;所得固体混合物置于管式气氛炉中,以8℃/min的升温速率加热至900℃,在氮气气氛下焙烧2h;所得焙烧产物,用足量的质量分数为10%的氢氟酸酸洗12h,采用足量的去离子水洗涤至pH为中性,60℃干燥8h后,得到所述CoSi双单原子催化剂。
实施例2:
本实施例制备MnSi双单原子催化剂。
将80g埃洛石均匀分散于1L水中,充分搅拌后,加入0.96g硝酸锰及8g苯胺,并采用、磷酸二氢钠和磷酸调节pH值至8;反应8h后,过滤,洗涤,并在80℃下干燥4h,得到固体混合物;所得固体混合物置于管式气氛炉中,以4℃/min的升温速率加热至800℃,在氮气气氛下焙烧2h;所得焙烧产物,用足量的质量分数为20%的盐酸酸洗8h,采用足量的去离子水洗涤至pH为中性,80℃干燥4h后,得到所述MnSi双单原子催化剂。
实施例3:
本实施例制备NiSi双单原子催化剂。
将50g粉石英均匀分散于1L水中,充分搅拌后,加入1.08g氯化镍及6g吡啶,并采用氢氧化钠调节浆料pH值至10;反应8h后,过滤,洗涤,并在40℃下干燥12h,得到固体混合物;所得固体混合物置于管式气氛炉中,以10℃/min的升温速率加热至1000℃,在氮气气氛下焙烧4h;所得焙烧产物,用足量的质量分数为5%的硫酸酸洗4h,采用足量的去离子水洗涤至pH为中性,40℃干燥12h后,得到所述NiSi双单原子催化剂。
实施例4:
本实施例制备CuSi双单原子催化剂。
将40g高岭石均匀分散于1L水中,充分搅拌后,加入0.86g硫酸铜及4g吡啶,并采用Tris-buffer调节浆料pH值至8.5;反应8h后,过滤,洗涤,并在70℃下干燥5h,得到固体混合物;所得固体混合物置于管式气氛炉中,以6℃/min的升温速率加热至600℃,在氮气气氛下焙烧2h;所得焙烧产物,用足量的质量分数为10%的氢氟酸酸洗12h,采用足量的去离子水洗涤至pH为中性,60℃干燥12h后,得到所述CoSi双单原子催化剂。
实施例5:
本实施例制备FeSi双单原子催化剂。
将70g蛭石均匀分散于1L水中,充分搅拌后,加入1.73g硝酸铁及15g盐酸多巴胺,并采用Tris-buffer调节浆料pH值至8.5;反应8h后,过滤,洗涤,并在50℃下干燥8h,得到固体混合物;所得固体混合物置于管式气氛炉中,以8℃/min的升温速率加热至900℃,在氮气气氛下焙烧2h;所得焙烧产物,用足量的质量分数为10%的氢氟酸酸洗12h,采用足量的去离子水洗涤至pH为中性,60℃干燥12h后,得到所述CoSi双单原子催化剂。
本发明的技术关键点在于:
1、本发明提供的MSi双单原子催化剂中过渡金属与硅以双单原子形式共同存在;
2、本发明提供的MSi双单原子催化剂保留了天然非金属矿物的微观形貌与多孔结构;
3、本发明提供的MSi双单原子催化剂活化过硫酸盐降解污染物效率高,稳定性好,重复使用性能优异,适用范围广,重金属离子二次污染风险低。
对比例1:
本对比例制备Co单原子催化剂。
将1.08g乙酸钴及10g盐酸多巴胺加入1L水中,并采用Tris-buffer调节浆料pH值至8.5;反应8h后,过滤,洗涤,并在60℃下干燥8h,得到固体混合物;所得固体混合物置于管式气氛炉中,以8℃/min的升温速率加热至900℃,在氮气气氛下焙烧2h;所得焙烧产物,用足量的质量分数为10%的氢氟酸酸洗12h,采用足量的去离子水洗涤至pH为中性,60℃干燥12h后,得到所述Co单原子催化剂。
参见附图1,为按实施1中技术方案制备的CoSi双单原子催化剂的球差电镜及相应元素面扫图,结果显示,Co与Si以双单原子形式存在于所述催化剂中。
参见附图2,为按实施1中技术方案制备的CoSi双单原子催化剂的X射线衍射图谱,结果显示,仅检测到归属于碳的石墨峰的(002)及(111)晶面的衍射峰,未出现与Co、Si元素相关的衍射峰。
试验例1:
以实施例1中技术方案制备的CoSi双单原子催化剂为例,与对比例1中所制备的催化剂在活化过硫酸盐降解双酚A废水中的应用对比研究,包括以下步骤:
准备两组100mL,20mg/L的双酚A废水,向两组体系中分别加入实施例1的CoSi双单原子催化剂(2mg)及对比例1的Co单原子催化剂(2mg),在暗处搅拌30min达到吸附平衡;再分别向两组体系中加入0.4mM过一硫酸钾(PMS)进行过硫酸盐活化反应,完成对双酚A废水的降解。
具体结果如图3所示,在6min内,实施例1的CoSi双单原子催化剂活化PMS,对双酚A的降解率高达98%,显著高于对比例1的Co单原子催化剂。
试验例2:
准备一组100mL,2mg/L的阿特拉津废水,向体系中加入实施例1的CoSi双单原子催化剂(2mg),在暗处搅拌30min达到吸附平衡;再向体系中加入0.4mM的PMS,活化反应6min后,完成对阿特拉津废水的降解。
具体结果如图4所示,在6min内,实施例1的CoSi双单原子催化剂活化PMS,对阿特拉津的降解率高达95%。
试验例3:
准备一组100mL,40mg/L的罗丹明B废水,向体系中加入实施例1的CoSi双单原子催化剂(2mg),在暗处搅拌30min达到吸附平衡;再向体系中加入0.4mM的PMS,活化反应6min后,完成对罗丹明B废水的降解。
具体结果如图4所示,在6min内,实施例1的CoSi双单原子催化剂活化PMS,对罗丹明B的降解率高达99%。
试验例4:
准备一组100mL,20mg/L的四环素废水,向体系中加入实施例1的CoSi双单原子催化剂(2mg),在暗处搅拌30min达到吸附平衡;再向体系中加入0.4mM的PMS,活化反应6min后,完成对四环素废水的降解。
具体结果如图4所示,在6min内,实施例1的CoSi双单原子催化剂活化PMS,对四环素的降解率高达97%。
试验例5:
不同实施例1的CoSi双单原子催化剂用量在活化过硫酸盐降解双酚A废水中的应用对比研究,包括以下步骤:
准备六组100mL,20mg/L的双酚A废水,分别向体系中加入不同质量的实施例1的CoSi双单原子催化剂(0.5mg、1.0mg、1.5mg、2.0mg、3.0mg及4.0mg),在暗处搅拌30min达到吸附平衡;再向体系中加入0.5mM的PMS进行过硫酸盐活化反应,完成对双酚A废水的降解。
具体结果如图5所示,当实施例1的CoSi双单原子催化剂用量大于1.5mg时,在6min内,实施例1的CoSi双单原子催化剂活化PMS,对双酚A的降解率已高达98%。
试验例6:
不同过一硫酸钾用量对于实施例1的CoSi双单原子催化剂在活化过硫酸盐降解双酚A废水中的影响研究,包括以下步骤:
准备六组100mL,20mg/L的双酚A废水,分别向体系中加入实施例1的CoSi双单原子催化剂(2mg),在暗处搅拌30min达到吸附平衡;再分别向体系中加入PMS(0.1mM、0.2mM、0.3mM、0.4mM、0.5mM及0.6mM)进行过硫酸盐活化反应,完成对双酚A废水的降解。
具体结果如图6所示,当PMS用量大于0.2mM时,在6min时,实施例1的CoSi双单原子催化剂活化PMS,对双酚A的降解率已高达90%。
试验例7:
不同反应pH值对于实施例1的CoSi双单原子催化剂在活化过硫酸盐降解双酚A废水中的影响研究,包括以下步骤:
准备八组100mL,20mg/L的双酚A废水,采用0.1M的盐酸及0.1M的氢氧化钠分别调节八组废水pH值至预设值(3、4、5、6、7、8、9、10),再分别向各体系中加入实施例1的CoSi双单原子催化剂(2mg),在暗处搅拌30min达到吸附平衡;再分别向体系中加入PMS(0.4mM)进行过硫酸盐活化反应,完成对双酚A废水的降解。
具体结果如图7所示,在不同反应pH值条件下,实施例1的CoSi双单原子催化剂活化PMS,对双酚A的降解率无显著差异,证明实施例1的CoSi双单原子催化剂广泛适用性。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节和这里示出与描述的实施例。
Claims (10)
1.一种非金属矿物诱导制备双单原子催化剂的方法,其特征在于,包括以下步骤:
步骤1、将天然非金属矿物均匀分散于水中,充分搅拌得到浆料,所述浆料中天然非金属矿物的浓度为40-90g/L;
步骤2、向步骤1所得的浆料中加入过渡金属盐和碳源,调节pH值至7-10,充分搅拌反应后,过滤、洗涤、干燥,得到固体混合物,所述过渡金属用量为0.86-1.73g/L,所述碳源用量为4-10g/L;
步骤3、将步骤2所得的固体混合物,进行焙烧处理,得焙烧产物;
步骤4、将步骤3所得的焙烧产物,进行酸洗,水洗至pH为中性,干燥后,得MSi双单原子催化剂,其中,M代表Co、Mn、Cu、Ni、Fe中的一种。
2.如权利要求1所述的非金属矿物诱导制备双单原子催化剂的方法,其特征在于,所述天然非金属矿物是膨润土、高岭石、硅藻土、蛭石、凹凸棒、海泡石、埃洛石、粉石英、沸石中的一种或两种。
3.如权利要求1所述的非金属矿物诱导制备双单原子催化剂的方法,其特征在于,所述过渡金属盐为钴盐、锰盐、镍盐、铜盐、铁盐中的一种;所述过渡金属盐的阴离子为硫酸根离子、氯离子、硝酸根离子、乙酸根离子中的一种。
4.如权利要求1所述的非金属矿物诱导制备双单原子催化剂的方法,其特征在于,所述碳源为苯胺、盐酸多巴胺、吡咯、吡啶中的一种或两种。
5.如权利要求1所述的非金属矿物诱导制备双单原子催化剂的方法,其特征在于,步骤2中,调节pH的调节剂为盐酸、硫酸、磷酸、氢氧化钠、磷酸二氢钠、Tris-buffer中的一种或多种。
6.如权利要求1所述的非金属矿物诱导制备双单原子催化剂的方法,其特征在于,步骤2中,所述干燥温度为40-80℃、时间为4-12h.。
7.如权利要求1所述的非金属矿物诱导制备双单原子催化剂的方法,其特征在于,步骤3中,所述焙烧处理温度为600-1000℃、时间为0.5-4h、升温速率为4-8℃/min;所述焙烧气氛为氩气、氮气、空气、氦气中的一种或两种。
8.如权利要求1所述的非金属矿物诱导制备双单原子催化剂的方法,其特征在于,步骤4中,所述酸洗中酸为硫酸、盐酸、氢氟酸、硝酸中的一种,所述酸的质量分数为5%-20%,所述酸洗时间为6-20h,所述干燥温度为40-80℃、时间为4-12h。
9.一种非金属矿物诱导制备得到的双单原子催化剂,其特征在于,由权利要求1~8任一项所述的非金属矿物诱导制备双单原子催化剂的方法制备而得。
10.一种如权利要求9所述的非金属矿物诱导制备得到的双单原子催化剂在活化过硫酸盐降解有机污染物中的应用,向待处理有机污染物中投加MSi双单原子催化剂及过硫酸盐,以去除有机污染物,所述过硫酸盐为过一硫酸钾、过硫酸钠、过硫酸铵、过二硫酸钾、过二硫酸钠、过硫酸铵中的一种或多种。
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