CN115487796B - 一种复合光催化剂及其制备方法和应用 - Google Patents
一种复合光催化剂及其制备方法和应用 Download PDFInfo
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- CN115487796B CN115487796B CN202211058343.4A CN202211058343A CN115487796B CN 115487796 B CN115487796 B CN 115487796B CN 202211058343 A CN202211058343 A CN 202211058343A CN 115487796 B CN115487796 B CN 115487796B
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- carbon
- titanium
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- hydrothermal
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Abstract
本发明属于空气净化技术领域,具体涉及一种复合光催化剂及其制备方法和应用。所述复合光催化剂以纳米水热碳为模板、钛盐为原料,采用液相吸附法得到水热碳吸附钛离子的前驱体,将前驱体置于惰性气氛中进行热处理以形成碳‑钛复合结构,最后将复合结构置于空气气氛中热暴露活化处理,即得到二氧化钛‑多孔碳一体化纳米多级结构的复合光催化剂。该方法可实现多孔碳和二氧化钛高暴露活性位多级结构的一体化成型,有效避免纳米颗粒堆积和团聚,同时实现多孔碳在多级结构中的均匀分布,使得多孔碳的吸附活性位点和二氧化钛的催化反应活性位点得到充分暴露,将其应用于挥发性有机物的吸附和光催化氧化中,具有优良的协同净化能力。
Description
技术领域
本发明属于空气净化技术领域,更具体地,涉及一种复合光催化剂及其制备方法和应用。
背景技术
当前,挥发性有机物(VOCs)是重要的大气污染物之一,不仅可以直接对人体健康产生持续危害,同时也是光化学烟雾、臭氧、二次有机气溶胶、细颗粒物(如PM2.5)等二次污染物的重要前驱体。因此,研究开发清洁高效、绿色低碳的大气VOCs污染控制技术成为目前研究的热点,这对于节能减排、践行绿色可持续发展及提高空气质量和人民健康水准具有重要意义。
在VOCs的污染控制技术中,光催化氧化具有绿色环保、节能低碳、设备简单和无二次污染等优点,尤其在净化处理低浓度VOCs方面具有较大的发展潜力。光催化净化效率与催化剂的结构特性存在密切关联,如催化剂的粒径、比表面积、孔径分布、堆积方式以及对VOCs吸附亲和性等均会影响VOCs的降解、转化产物类型及矿化过程。中国专利申请CN109219577A公开了一种由水解的酸性钛氧化合物获得以团聚形式的纳米颗粒二氧化钛的方法,但是其中纳米颗粒密集堆积或团聚的催化剂不能与VOCs分子充分接触,导致VOCs停留时间短、氧化自由基的形成效率低等,造成VOCs不能被有效的降解和矿化,甚至形成高沸点转化产物致使催化剂存在失活风险。
发明内容
本发明要解决的技术问题是克服现有传统二氧化钛纳米颗粒由于其密集堆积或团聚不能与VOCs分子充分接触,导致VOCs停留时间短、氧化自由基的形成效率低等,造成VOCs不能被有效的降解和矿化,甚至形成高沸点转化产物致使催化剂存在失活风险的缺陷和不足,提供一种复合光催化剂的制备方法。
本发明另一目的是提供一种复合光催化剂。
本发明再一目的是提供一种复合光催化剂在作为VOCs选择性吸附剂或光催化剂中的应用。
本发明上述目的通过以下技术方案实现:
一种复合光催化剂的制备方法,包括以下步骤:
S1.以纳米水热碳为模板,钛盐为原料,醇溶液为溶剂,采用液相吸附法获得水热碳吸附钛离子的前驱体;
S2.将步骤S1所得前驱体在惰性气体保护下200~950℃进行热处理,得到碳-钛复合物;
S3.将步骤S2所得碳-钛复合物置于一定氧气体积比的空气气氛中,180~500℃暴露热活化处理,即得。
进一步地,所述暴露热活化温度为180~500℃时,所述钛盐中钛的物质的量与纳米水热碳的质量的比例为1×10-2~12×10-2mol/g。
优选地,当所述暴露热活化处理的温度为180~450℃,所述钛盐中钛的物质的量与纳米水热碳的质量的比例为2×10-2~12×10-2mol/g。
进一步地,步骤S3中,所述暴露热活化处理的保持时间为0.1~10h。
优选地,当所述暴露热活化处理的温度为450~500℃,所述暴露热活化处理的保持时间为0.1~2h。
进一步地,步骤S3中,所述氧气体积比为1%~21%。
优选地,当所述暴露热活化处理的温度为450~500℃,所述氧气体积比为1%~15%。
具体地,步骤S1中,所述纳米水热碳的制备方法包括以下步骤:采用果糖、葡萄糖、蔗糖中的一种或多种为碳源,通过第一次水热法得到糖的碳化物,将所得碳化物为种子进行第二次水热法,即得。
进一步地,所述第一次水热法的反应温度为130~170℃。
进一步地,所述第一次水热法的升温速率为0.1~1℃/min。
进一步地,所述第二次水热法的反应温度为160~190℃。
进一步地,所述第二次水热法的升温速率为1~5℃/min。
进一步地,所述第一次水热法和第二次水热法的反应时间均为5~15h。
本发明通过一种简单有效的方法即可稳定获得具有二氧化钛-多孔碳一体化纳米多级结构的复合光催化剂,有效避免二氧化钛纳米颗粒的团聚,同时实现多孔碳在多级结构中的均匀分布,其孔径以介孔为主,为VOCs的吸附传质和光催化氧化反应提供丰富的活性位点,集吸附和催化性能于一体,在光照的条件下能够产生大量的氧化自由基如羟基自由基和超氧自由基,大幅度促进富集于光催化表面的挥发性有机物的降解氧化,可避免因界面传质问题造成产物累积、催化剂失活等问题,有效促进挥发性有机物的吸附和反应过程,充分发挥多孔碳和二氧化钛对挥发性有机物的协同净化能力。
进一步地,步骤S1中,所述纳米水热碳含有丰富的含氧类官能团。
进一步地,步骤S1中,所述纳米水热碳的晶体结构为无定形,形貌结构为树枝状结构、球形颗粒或球形颗粒的交联结构的一种或多种。
进一步地,步骤S1中,所述钛盐选自硫酸氧钛、四氯化钛、钛酸四丁酯中的一种或多种。
进一步地,步骤S1中,所述醇溶液中的醇为甲醇、乙醇、乙二醇、丙三醇的一种或多种;所述钛盐直接溶于水中会导致钛离子水解过快形成较大的团聚体,并且水的表面张力大,不利于金属离子的渗透吸附,利用醇溶液溶解钛盐可以解决所述问题。
优选地,步骤S1中,所述钛盐溶于醇溶液后的浓度为0.01mol/L~2mol/L。
进一步地,步骤S1中,所述液相吸附法为搅拌吸附或浸渍吸附,吸附过程均在室温条件下进行。
更进一步地,步骤S1中,所述液相吸附法的前处理方式为:采用搅拌吸附,则水热碳需要与钛盐的醇水溶液形成均一混悬液,或采用浸渍吸附时,则水热碳需要抽滤成饼以形成三维结构进行浸渍吸附。
优选地,所述搅拌吸附的吸附时间为1~24h,或浸渍吸附的浸渍时间为0.5~24h。
优选地,步骤S2中,所述惰性气体为氩气或氮气,
优选地,步骤S2中,所述惰性气体的流速为10~100mL/min。
优选地,步骤S2中,所述热处理的升温速率为1~20℃/min。
优选地,步骤S2中,所述热处理的处理时间为0.5~10h。
优选地,步骤S3中,所述暴露热活化处理的升温速率为1~20℃/min。
另外的,本发明提供了由上述制备方法制备得到的复合光催化剂。
进一步地,所述复合光催化剂的基本形貌为二氧化钛-多孔碳一体化纳米多级结构。
更进一步地,所述复合光催化剂的基本形貌为中空树枝状、带状多级孔结构或无序多级孔结构的一种或多种。
优选地,所述复合光催化剂中碳的形态为无定性碳、石墨型碳的一种或两种。
本发明还提供了所述复合光催化剂在降解挥发性有机物中的应用。
进一步地,所述挥发性有机物为苯系物、醛类、酯类、酮类、卤代烃。
优选地,所述苯系物为苯、甲苯、乙苯、二甲苯、苯乙烯。
优选地,所述醛类为甲醛、乙醛。
优选地,所述酯类为乙酸乙酯、乙酸丁酯。
优选地,所述酮类为丙酮、异丁酮。
优选地,所述卤代烃为二氯甲烷、三氯甲烷。
本发明具有以下有益效果:
本发明通过一种简单有效的方法即可稳定获得具有二氧化钛-多孔碳一体化纳米多级结构的复合光催化剂,有效避免二氧化钛纳米颗粒的团聚,同时实现多孔碳在多级结构中的均匀分布,且该纳米多级结构具有颗粒尺寸小、比表面积大以及丰富的吸附和催化氧化反应活性位点,可有效促进挥发性有机物的吸附和催化反应过程,通过二氧化钛和多孔碳的协同作用可为挥发性有机物的吸附传质、降解和矿化提供丰富的活性位点,在一定条件下,可以稳定、持久地吸附-光催化氧化一体化氧化降解挥发性有机物,充分发挥多孔碳和二氧化钛对甲苯的协同净化能力。另外,复合光催化剂可通过简单的光照产生活性氧自由基实现对其界面的残留的碳质进行氧化分解和活化再生,避免了催化剂固体废弃物的处置和二次污染物的产生问题。
附图说明
图1为本发明实施例1制备的复合光催化剂的扫描电镜图;
图2为本发明实施例1制备的复合光催化剂的比表面积和孔径分布图;
图3(a)为本发明实施例1制备的复合光催化剂对甲苯的吸附图,图3(b)为本发明实施例2制备的复合光催化剂对甲苯的催化降解曲线图;
图4(a)为本发明实施例4制备的复合光催化剂对甲苯的吸附图,图4(b)为本发明实施例4制备的复合光催化剂对甲苯的催化降解曲线图;
图5为本发明实施例3制备的复合光催化剂的元素分布图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
本发明实施例1~4中所采用纳米水热碳参考中国专利申请CN113697794A实施例2的制备方法制备得到,包括以下步骤:
称取20g的葡萄糖加入到80mL的乙醇水溶液中(乙醇和水的体积比为3:2),采用超声分散溶解可得到澄清透明的葡萄糖乙醇水溶液;将葡萄糖乙醇水溶液转移至聚四氟乙烯衬底的高压反应釜中,以0.2℃/min的升温速率升温至165℃,恒温反应8h后,自然冷却至室温,可得到棕红色半透明的葡萄糖的高浓度碳化物种子;采用移液枪量取25mL的葡萄糖的高浓度碳化物种子于70mL的乙醇水溶液(乙醇和水的体积比为1:20)中得到均相的混合溶液,将混合溶液转移至聚四氟乙烯衬底的高压反应釜中,以4℃/min的升温速率逐渐升至180℃,反应10h,自然冷却至室温,可得到棕色悬浊产物,以乙醇为洗涤剂,将产物采用离心机在11000r/min的条件下离心洗涤3~4次,然后置于冷冻干燥机中处理15h,即可获得树枝状超细水热碳粉末。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1一种复合光催化剂的制备
一种复合光催化剂的制备,包括以下步骤:
S1.称取0.1g纳米水热碳;
S2.将上述水热碳分散于8mL的0.5mol/L的TiCl4的乙醇溶液中形成均一的混悬液,接着在室温条件下搅拌吸附12h;
S3.将上述样品离心,分别采用乙醇和去离子水洗涤,冻干处理10h得到水热碳吸附钛离子的前驱体;
S4.将上述前驱体置于管式炉中,以流速为30mL/min的氩气为保护气,设置升温速率为5℃/min,逐步升温至500℃并保持4h,可得到碳-钛复合物;
S5.将上述的碳-钛复合物重新置于马弗炉中,设置空气中氧气的体积比为21%,以1℃/min的升温速率逐步升至400℃并保持2h,即可获得具有二氧化钛-多孔碳一体化纳米多级结构的复合光催化剂。
实施例2一种复合光催化剂的制备
一种复合光催化剂的制备,包括以下步骤:
S1.称取0.1g纳米水热碳;
S2.将上述水热碳分散于8mL的0.5mol/L的TiCl4的乙醇溶液形成均一的混悬液,接着在室温条件下搅拌吸附12h;
S3.将上述样品离心,分别采用乙醇和去离子水洗涤,冻干处理10h得到水热碳吸附钛离子的前驱体;
S4.将上述前驱体置于管式炉中,以流速为30mL/min的氩气为保护气,设置升温速率为5℃/min,逐步升温至500℃并保持4h,可得到碳-钛复合物;
S5.将上述的碳-钛复合物重新置于马弗炉中,设置空气中氧气的体积比为21%,以1℃/min的升温速率逐步升至450℃并保持2h,即可获得具有二氧化钛-多孔碳一体化纳米多级结构的复合光催化剂。
实施例3一种复合光催化剂的制备
一种复合光催化剂的制备,包括以下步骤:
S1.称取0.1g纳米水热碳;
S2.将上述水热碳分散于8mL的1mol/L的TiCl4的乙醇溶液形成均一的混悬液,接着在室温条件下搅拌吸附12h;
S3.将上述样品离心,分别采用乙醇和去离子水洗涤,冻干处理10h得到水热碳吸附钛离子的前驱体;
S4.将上述前驱体置于管式炉中,以流速为30mL/min的氩气为保护气,设置升温速率为5℃/min,逐步升温至500℃并保持4h,可得到碳-钛复合物;
S5.将上述的碳-钛复合物重新置于马弗炉中,设置空气中氧气的体积比为21%,以1℃/min的升温速率逐步升至500℃并保持2h,即可获得具有二氧化钛-多孔碳一体化纳米多级结构的复合光催化剂。
实施例4一种复合光催化剂的制备
一种复合光催化剂的制备,包括以下步骤:
S1.称取0.1g纳米水热碳;
S2.将上述水热碳分散于8mL的0.5mol/L的TiCl4的乙醇溶液形成均一的混悬液,接着在室温条件下搅拌吸附12h;
S3.将上述样品离心,分别采用乙醇和去离子水洗涤,冻干处理10h得到水热碳吸附钛离子的前驱体;
S4.将上述前驱体置于管式炉中,以流速为30mL/min的氩气为保护气,设置升温速率为5℃/min,逐步升温至500℃并保持4h,可得到碳-钛复合物;
S5.将上述的碳-钛复合物重新置于马弗炉中,设置空气中氧气的体积比为21%,以1℃/min的升温速率逐步升至500℃并保持2h,即可获得具有二氧化钛-多孔碳一体化纳米多级结构的复合光催化剂。
实验例
测定实施例1制备的复合光催化剂的扫描电镜图,结果如图1所示,所得复合光催化剂为带状交织的纳米多级结构,整体纳米多级结构具有丰富的孔结构,可为VOCs的光催化氧化反应提供丰富的活性位点;实施例2和实施例3中所制备的复合光催化剂的扫描电镜图与实施例1基本一致;
测定实施例1制备的复合光催化剂的比表面积和孔径,结果如图2所示,具有一体化纳米多级结构的复合光催化剂的比表面积可达140.97m2/g,平均孔径为5.64nm,主要以介孔为主;实施例2和实施例3中所制备的复合光催化剂的比表面积和孔径结果与实施例1基本一致;
采用连续相光催化反应系统评价实施例1制备的复合光催化剂对甲苯的吸附性能,用质量流量计控制甲苯和载气的流量为30mL/min,称取40mg制备的复合光催化剂进行吸附实验,结果如图3a所示,复合光催化剂对甲苯的饱和吸附时间超过600min(甲苯浓度40ppmv),说明该条件下制备的复合光催化剂可为甲苯的吸附传质提供丰富的活性位点;
模拟太阳光照下,利用实施例2所制备的复合光催化剂进行甲苯的催化降解性能测试,首先进行加热脱气预处理,除去催化剂孔道表面的水和杂质,然后在通入40ppmv甲苯气,吸附至饱和后,使用300W汞灯模拟太阳光条件下、间距为12cm进行光照催化,结果如图3b示,光照350min后催化剂对甲苯的降解效率仍能稳定在95%,说明该复合光催化剂具有较高的催化氧化活性和稳定性能,同时也说明该复合光催化剂可为甲苯的吸附传质提供丰富的吸附和反应活性位点,在光照的条件下能够产生大量的氧化自由基如羟基自由基和超氧自由基,大幅促进富集于光催化表面的甲苯的降解氧化,可避免因界面传质问题造成产物累积、催化剂失活等问题;实施例3中所制备的复合光催化剂对甲苯的吸附性能和催化降解性能的测试效果与实施例1和2的基本一致;
测试实施例4所制备的复合光催化剂对甲苯的吸附性能和催化降解性能,结果分别如图4(a)和图4(b)所示,该条件下制备的复合光催化剂活性剂吸附性能和光催化性能较差:对甲苯的吸附容量为4mg/g,对比实施例1,仅有其10%的吸附容量;在30mL/min、40ppmv浓度条件下光催化降解,其活性逐渐降低,300min后对甲苯的降解效率降至40%;其性能较差主要由煅烧过程中暴露温度过高,并且钛盐负载量较低,二氧化钛-多孔碳纳米多级结构形成较大的团聚体,导致其吸附和催化活性位点减少,不能有效促进挥发性有机物的吸附和反应过程,降低了多孔碳和二氧化钛对甲苯的协同净化能力。另外,当煅烧温度过高时,需要相对应减少煅烧的时间和空气中氧气的体积比,以减少高温引起的碳的消耗和二氧化钛的团聚,所得的复合光催化剂才能实现较好的吸附降解效果。
采用扫描电镜的EDS面扫对实施例3所制备的复合光催化剂的基本组成进行分析,结果如图5所示,二氧化钛和多孔碳呈现明显的一体化均匀分布,这种高度均一的分布状态可有效避免纳米颗粒堆积和团聚,同时实现多孔碳在多级结构中的均匀分布,使得多孔碳的吸附活性位点和二氧化钛的催化反应活性位点得到充分暴露,有效促进挥发性有机物的吸附和反应过程,大幅增强多孔碳和二氧化钛对甲苯的协同净化能力;实施例1和实施例2中所制备的复合光催化剂扫描电镜的EDS面扫结果与实施例3基本一致;
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
1.一种复合光催化剂的制备方法,其特征在于,包括以下步骤:
S1 .以纳米水热碳为模板,钛盐为原料,醇溶液为溶剂,采用液相吸附法获得水热碳吸附钛离子的前驱体;
S2 .将步骤S1所得前驱体在惰性气体保护下200~950℃进行热处理,得到碳-钛复合物;
S3 .将步骤S2所得碳-钛复合物置于一定氧气体积比的空气气氛中,180~500℃暴露热活化处理,即得;
其中,步骤S1中,所述纳米水热碳采用果糖、葡萄糖、蔗糖中的一种或多种为碳源通过水热法制备得到;
所述氧气体积比为1%~21%;
所述钛盐选自硫酸氧钛、四氯化钛、钛酸四丁酯中的一种或多种。
2.根据权利要求1所述制备方法,其特征在于,当所述暴露热活化温度为180~500℃时,所述钛盐中钛的物质的量与纳米水热碳的质量的比例为1×10-2~12×10-2mol/g。
3.根据权利要求1所述制备方法,其特征在于,步骤S1中,所述液相吸附法为搅拌吸附或浸渍吸附,吸附过程均在室温条件下进行。
4.根据权利要求1所述制备方法,其特征在于,步骤S2中,所述热处理的升温速率为1~20℃/min。
5.根据权利要求1所述制备方法,其特征在于,步骤S3中,所述暴露热活化处理的升温速率为1~20℃/min。
6.根据权利要求1所述制备方法,其特征在于,步骤S3中,所述暴露热活化处理的保持时间为0.1~10h。
7.一种根据权利要求1~6任一所述制备方法制备的复合光催化剂。
8.一种根据权利要求7所述复合光催化剂在降解挥发性有机物中的应用。
9.根据权利要求8所述应用,其特征在于,所述挥发性有机物为苯系物、醛类、酯类、酮类、卤代烃。
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