CN110639560A - 一种复合卤氧化铋光催化剂及其制备方法和应用 - Google Patents
一种复合卤氧化铋光催化剂及其制备方法和应用 Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 33
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 230000031700 light absorption Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 6
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- 238000013329 compounding Methods 0.000 abstract description 2
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 37
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 22
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- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- OLBRKKJBIBPJSE-UHFFFAOYSA-N bismuth;bromo hypobromite Chemical class [Bi].BrOBr OLBRKKJBIBPJSE-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
本发明涉及一种复合卤氧化铋光催化剂及其制备方法和应用,所述卤氧化铋表面复合有Co9S8,所述卤氧化铋的化学式为BiOX,其中,X为Cl、Br和I中的一种或几种。Co9S8具有带隙窄、电荷转移效率高、导带位置高等优点,与BiOX复合形成Z型异质结,既能够降低BiOX光生电子与空穴的复合几率,提升电子空穴的利用效率,又能增强BiOX的氧化还原能力,利用光催化‑吸附协同效应提升了对废水中重金属的去除率。
Description
技术领域
本发明涉及催化剂领域,具体涉及一种复合卤氧化铋光催化剂及其制备方法和应用。
背景技术
随着工业化进程的深入,环境中重金属废水污染日益加剧,重金属(如含镉、镍、汞、锌等)废水是对环境污染最严重和对人类危害最大的工业废水之一。废水中的重金属一般不能分解破坏,只能转移其存在位置和转变其物化形态。目前,依靠的传统的方法(物理处理法、化学处理法和生物处理法等)处理这些废水因其造价较高、过程复杂且效果不佳而受到一定的制约性。近年来发展的半导体光催化方法具有成本低、效率高、不产生二次污染等优点,因此被广泛认为是一种前景极大的去除方法。
卤氧化铋(BiOX,X=Cl、Br、I)是一种半导体材料,具有可见光响应的光催化性能,且具有独特的电子结构,即卤素原子(Cl、Br、I)位于(Bi2O2)2+层之间,(Bi2O2)2+正极层与带负电的卤素原子之间形成内部电场,内部电场的性成能够有效地分离光生电子空穴对。但卤氧化铋存在吸光效率低、光生电荷转移效率低、光催化活性差、光催化性能稳定性差的缺点,不利于光催化剂的光能转化,从而限制了此材料的应用。为了提高卤氧化铋的光催化性能,已有科研工作者对其进行改性,如中国专利文献CN107961800A公开了一种碘化银纳米粒修饰溴氧化铋复合光催化剂,该催化剂为球状,直径为2μm~4μm,该催化剂处理有机废水效果较好,但成本较高且处理无机废水时效果不太理想。
发明内容
因此,本发明要解决的技术问题在于克服现有技术中碘化银纳米粒修饰溴氧化铋复合光催化剂的成本较高且处理无机废水效果不理想的缺陷,从而提供一种复合卤氧化铋光催化剂。
本发明还提供一种复合卤氧化铋光催化剂的制备方法。
本发明还提供一种复合卤氧化铋光催化剂的应用。
为此,本发明提供一种复合卤氧化铋光催化剂,所述卤氧化铋表面复合有Co9S8,所述卤氧化铋的化学式为BiOX,其中,X为Cl、Br和I中的一种或几种。
进一步地,所述光催化剂为纳米片状,直径为300~500nm,厚度为25~50nm,比表面积为5.83~7.73m2/g,平均孔径为18.49~33.48nm,光吸收带边在350~700nm,带隙能为2.37~3.49eV,Co9S8与BiOX的摩尔比为(0.05~0.3):1。
进一步地,所述光催化剂为Z型异质结结构。
本发明还提供一种复合卤氧化铋光催化剂的制备方法,包括以下步骤:
a)将铋源加入到醇和水的混合溶液中,得混合液a;
b)向所述混合液a中加入卤源,进行水热反应,冷却后进行过滤、洗涤、干燥,得到BiOX;以及
c)将钴源和硫源溶于水中,然后加入表面活性剂和所述BiOX,得混合液b,将所述混合液b进行水热反应,反应完成后冷却、洗涤、干燥得到Co9S8/BiOX复合光催化剂。
进一步地,所述醇为乙二醇、1,3-丙二醇和聚乙二醇中的一种或几种;所述表面活性剂为非离子表面活性剂,具体可以为聚乙烯吡咯烷酮、聚乙烯醇和聚丙烯酰胺中的一种或几种。
进一步地,所述铋源为硝酸铋和/或硫酸铋;所述卤源为氯化钠、氯化钾、溴化钠、溴化钾、碘化钠和碘化钾中的一种或几种;所述钴源为氯化钴和/或硝酸钴;所述硫源为硫脲、硫代乙酰胺和硫化钠中的一种或几种。
进一步地,所述钴源与所述硫源的摩尔比为1:(2~6)。
进一步地,所述步骤b)中水热反应条件为140~180℃下水热反应10~18小时;所述步骤c)中水热反应条件为160~180℃反应0.5~2h。
进一步地,所述步骤b)和所述步骤c)中的所述洗涤为用丙酮、乙醇及去离子水交替多次洗涤。
本发明还提供一种所述的复合卤氧化铋光催化剂在废水处理中的应用。
进一步地,所述废水为无机废水。
本发明技术方案,具有如下优点:
1.本发明提供的Co9S8复合BiOX光催化剂,通过窄带隙的Co9S8与宽带隙的BiOX耦合后,Co9S8表面的正电位在废水溶液中会对含重金属的负离子具有较强的吸附能力,从而使Co9S8/BiOX复合物同样对重金属负离子具有吸附能力,并且,Co9S8具有带隙窄、电荷转移效率高、导带位置高等优点,与BiOX复合,既能够降低BiOX光生电子与空穴的复合几率,提升电子空穴的利用效率,又能增强BiOX的氧化还原能力,利用光催化-吸附协同效应提升了对废水中重金属的去除率。
2.本发明提供的Co9S8复合BiOX光催化剂形成的是Z型异质结,这种结构可以得到更强的氧化还原性能,促进电子空穴对的分离,提升光生电子的有效利用。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为实施例1制得的催化剂A的扫描电子显微镜图;
图2a为实施例1制得的催化剂A的透射电镜图;
图2b为图2a中A部分的局部放大图;
图3为本发明制备的Z型Co9S8/BiOCl光催化剂的XRD图谱;
图4a为本发明制备的Z型Co9S8/BiOCl光催化剂的光吸收图;
图4b为本发明制备的Z型Co9S8/BiOCl光催化剂的带隙图;
图5为本发明制备的Z型Co9S8/BiOCl光催化剂的结构模拟机理图;
图6为本发明制备的Z型Co9S8/BiOCl光催化剂在模拟太阳光下对Cr(VI)的去除率图。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品。
实施例1
(a)取2.4254g硝酸铋加入乙二醇与水的混合溶液中,混合溶液的体积为40mL,乙二醇与水的体积比为2:3,超声搅拌后得到均匀混合液a;
(b)向混合液a中滴入40mL浓度为7.3125g/L的氯化钠溶液,室温搅拌均匀后得到乳白色浊液,继续搅拌5小时,再将乳白色浊液在140℃下水热反应10小时,冷却后,将反应产物依次进行过滤、洗涤(丙酮,乙醇及去离子水交替洗涤3次)、干燥(60℃,8h)即得BiOCl光催化剂;
(c)取0.1310g硝酸钴和0.2055g硫脲加入到30mL去离子水中,混合均匀后,得到紫色透明混合溶液;向紫色透明混合溶液中加入0.1g聚乙烯吡咯烷酮K30以及1mmol制备好的BiOCl,继续搅拌及超声分散之后,转移至聚四氟乙烯内衬的PEEK消解罐中,再置于微波水热合成仪内,设置程序升温至160℃反应1h,将反应产物依次进行过滤、洗涤(丙酮,乙醇及去离子水交替洗涤3次)、真空干燥(60℃,8h),即得Z型Co9S8/BiOCl光催化剂,即为催化剂A。
实施例1制得的Z型结构Co9S8复合BiOCl纳米片光催化剂的扫描电镜图见图1,透射电镜图见图2a和图2b,可以看出,催化剂形貌为纳米片,片状上的小黑点为Co9S8。
采用比表面积测定仪进行比表面积性能测试,测试结果显示,制得的光催化剂的比表面积为5.83m2/g,平均孔径为33.48nm。
采用固体紫外分光光度计对所制备的光催化剂进行测试,发现该光催化剂的带隙能为3.04eV。
实施例2
(a)取1.7653g硫酸铋加入1,3-丙二醇与水的混合溶液中,混合溶液的体积为40mL,1,3-丙二醇与水的体积比为2:3,超声搅拌后得到均匀混合液a;
(b)向混合液a中滴入40mL浓度为9.3125g/L的氯化钾溶液,室温搅拌均匀后得到乳白色浊液,继续搅拌5小时,再将乳白色浊液在180℃下水热反应15小时,冷却后,将反应产物依次进行过滤、洗涤(丙酮,乙醇及去离子水交替洗涤3次)、干燥(60℃,8h)即得BiOCl光催化剂;
(c)取0.2142g氯化钴和0.4057g硫代乙酰胺加入到30mL去离子水中,混合均匀后,得到紫色透明混合溶液;向紫色透明混合溶液中加入0.1g聚乙烯醇PVA-150以及1mmol制备好的BiOCl,继续搅拌及超声分散之后,转移至聚四氟乙烯内衬的PEEK消解罐中,再置于微波水热合成仪内,设置程序升温至180℃反应0.5h,将反应产物依次进行过滤、洗涤(丙酮,乙醇及去离子水交替洗涤3次)、真空干燥(60℃,8h),即得Z型Co9S8/BiOCl光催化剂,即为催化剂B。
采用比表面积测定仪进行比表面积性能测试,测试结果显示,催化剂B的比表面积为6.27m2/g,平均孔径为32.31nm。
采用固体紫外分光光度计对所制备的光催化剂进行测试,发现催化剂B的带隙能为2.45eV。
实施例3
(a)取2.4254g硝酸铋加入聚乙二醇与水的混合溶液中,混合溶液的体积为40mL,聚乙二醇与水的体积比为2:3,超声搅拌后得到均匀混合液a;
(b)向混合液a中滴入40mL浓度为7.3125g/L的氯化钾溶液,室温搅拌均匀后得到乳白色浊液,继续搅拌5小时,再将乳白色浊液在160℃下水热反应18小时,冷却后,将反应产物依次进行过滤、洗涤(丙酮,乙醇及去离子水交替洗涤3次)、干燥(60℃,8h)即得BiOCl光催化剂;
(c)取0.5240g硝酸钴和2.5936g硫化钠加入到30mL去离子水中,混合均匀后,得到紫色透明混合溶液;向紫色透明混合溶液中加入0.001g聚丙烯酰胺以及1mmol制备好的BiOCl,继续搅拌及超声分散之后,转移至聚四氟乙烯内衬的PEEK消解罐中,再置于微波水热合成仪内,设置程序升温至170℃反应2h,将反应产物依次进行过滤、洗涤(丙酮,乙醇及去离子水交替洗涤3次)、真空干燥(60℃,8h),即得Z型Co9S8/BiOCl光催化剂,即为催化剂C。
采用比表面积测定仪进行比表面积性能测试,测试结果显示,催化剂C的比表面积为7.47m2/g,平均孔径为31.87nm。
采用固体紫外分光光度计对所制备的光催化剂进行测试,发现催化剂C的带隙能为2.37eV。
实施例4
取0.7860g硝酸钴和1.2330g硫脲,其余与实施例1相同。制得的Z型Co9S8/BiOCl光催化剂,记为催化剂D。
采用比表面积测定仪进行比表面积性能测试,测试结果显示,催化剂D的比表面积为6.23m2/g,平均孔径为32.83nm。
采用固体紫外分光光度计对所制备的光催化剂进行测试,发现催化剂D的带隙能为2.38eV。
实施例5
步骤(b)中浓度为7.3125g/L的氯化钠溶液换为浓度为12.8744g/L的溴化钠,其余与实施例1相同。制得的Z型Co9S8/BiOBr光催化剂,记为催化剂E。
实施例6
步骤(b)中浓度为7.3125g/L的氯化钠溶液换为浓度为18.7555g/L的碘化钠,其余与实施例1相同。制得的Z型Co9S8/BiOBr光催化剂,记为催化剂F。
对比例1
制备BiOCl光催化剂:制备方法同实施例1。
对比例2
制备的Co9S8光催化剂:取2.6200g硝酸钴和4.110g硫脲,不添加BiOCl,其他操作步骤同实施例1。
采用X射线衍射(XRD)对实施例1~4得到的催化剂A~D及对比例1和2的催化剂进行分析,图3为上述催化剂的XRD图谱,从图中衍射角2θ=11.99°、24.19°、25.94°、32.47°、33.42°、40.98°、46.65°、49.78°、54.06°、55.15°、58.64°处衍射峰对应于四方晶体系BiOCl的(001)、(002)、(101)、(110)、(102)、(112)、(200)、(113)、(211)、(104)、(212)晶面,实施例1~4得到的催化剂A~D在2θ=15.46°、29.86°处的衍射峰对应于立方晶体系Co9S8的(111)和(311)晶面,说明成功制备了Co9S8复合BiOCl光催化剂。
采用X射线衍射(XRD)对实施例1~4得到的催化剂A~D及对比例1和2的催化剂进行分析,图4a和图4b分别为上述催化剂的光吸收图及对应的带隙图,说明复合Co9S8提升了BiOCl的光吸收能力。
对实施例1-4及对比例1-2所制得的催化剂进行活性和稳定性测试,具体测试方法及数据如下:
一.催化剂活性测试
1.模拟太阳光(400W金卤灯)下,取25mg实施例1-4以及对比例1-2的催化剂分别加入50mL Cr(VI)浓度为10ppm水溶液中,光照2h后,测试水溶液中Cr(VI)的去除率,结果见表1及图6:
表1不同催化剂活性测试结果
二.催化剂稳定性测试
模拟太阳光(400W金卤灯)下,将30mg本发明实施例2的催化剂B加入到50mL Cr(VI)浓度为10ppm的水溶液进行光催化反应,在下一次反应中的催化剂为上一次反应所用催化剂用去离子水和乙醇交替洗涤,然后60℃下过夜干燥处理得到的,结果见下表2所示:
表2催化剂B稳定性测试结果
从上表2中的数据可知,Z型Co9S8/BiOCl光催化剂在多次循环利用后,对水体中Cr(VI)去除率仍然高,表明催化剂稳定性高。
实施例与对比例在同一条件下进行活性测试评价,实施例1~4得到的催化剂A~D相对于对比例1去除废水中的重金属有毒离子Cr6+总效率分别提升了15.5%、37.1%、51.8%和46.6%,实施例1~4得到的催化剂A~D相对于对比例2去除废水中的重金属有毒离子Cr6+总效率分别提升了5.7%、27.3%、42%和36.8%。可见,利用光催化-吸附协同效应提升了对废水种重金属的去除效率。本发明合成工艺简单,成本较低,催化效率高,符合实际生产需求,在光催化领域具有广泛的应用前景。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (11)
1.一种复合卤氧化铋光催化剂,其特征在于,所述卤氧化铋表面复合有Co9S8,所述卤氧化铋的化学式为BiOX,其中,X为Cl、Br和I中的一种或几种。
2.根据权利要求1所述的复合卤氧化铋光催化剂,其特征在于,所述光催化剂为纳米片状,直径为300~500nm,厚度为25~50nm,比表面积为5.83~7.73m2/g,平均孔径为18.49~33.48nm,光吸收带边在350~700nm,带隙能为2.37~3.49eV,Co9S8与BiOX的摩尔比为(0.05~0.3):1。
3.根据权利要求2所述的复合卤氧化铋光催化剂,其特征在于,所述光催化剂为Z型异质结结构。
4.一种复合卤氧化铋光催化剂的制备方法,其特征在于,包括以下步骤:
a)将铋源加入到醇和水的混合溶液中,得混合液a;
b)向所述混合液a中加入卤源,进行水热反应,冷却后进行过滤、洗涤、干燥,得到BiOX;以及
c)将钴源和硫源溶于水中,然后加入表面活性剂和所述BiOX,得混合液b,将所述混合液b进行水热反应,反应完成后冷却、洗涤、干燥得到Co9S8/BiOX复合光催化剂。
5.根据权利要求4所述的复合卤氧化铋光催化剂的制备方法,其特征在于,所述醇为乙二醇、1,3-丙二醇和聚乙二醇中的一种或几种;所述表面活性剂为非离子表面活性剂。
6.根据权利要求5所述的复合卤氧化铋光催化剂的制备方法,其特征在于,所述铋源为硝酸铋和/或氯化铋;所述卤源为氯化钠、氯化钾、溴化钠、溴化钾、碘化钠和碘化钾中的一种或几种;所述钴源为氯化钴和/或硝酸钴;所述硫源为硫脲、硫代乙酰胺和硫化钠中的一种或几种。
7.根据权利要求6所述的复合卤氧化铋光催化剂的制备方法,其特征在于,所述钴源与所述硫源的摩尔比为1:(2~6)。
8.根据权利要求7所述的复合卤氧化铋光催化剂的制备方法,其特征在于,所述步骤b)中水热反应条件为140~180℃下水热反应10~18小时;所述步骤c)中水热反应条件为160~180℃反应0.5~2h。
9.根据权利要求8所述的复合卤氧化铋光催化剂的制备方法,其特征在于,所述步骤b)和所述步骤c)中的所述洗涤为用丙酮、乙醇及去离子水交替多次洗涤。
10.权利要求1~9任一项所述的复合卤氧化铋光催化剂在废水处理中的应用。
11.根据权利要求10所述的复合卤氧化铋光催化剂在废水处理中的应用,其特征在于,所述废水为无机废水。
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