CN111644170A - 一种在可见光照射下具有优异光催化性能的棒状铈掺杂氧化锌与石墨烯复合材料光催化剂 - Google Patents
一种在可见光照射下具有优异光催化性能的棒状铈掺杂氧化锌与石墨烯复合材料光催化剂 Download PDFInfo
- Publication number
- CN111644170A CN111644170A CN202010040052.7A CN202010040052A CN111644170A CN 111644170 A CN111644170 A CN 111644170A CN 202010040052 A CN202010040052 A CN 202010040052A CN 111644170 A CN111644170 A CN 111644170A
- Authority
- CN
- China
- Prior art keywords
- solution
- minutes
- stirring
- sample
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000013507 mapping Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 238000000862 absorption spectrum Methods 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000002835 absorbance Methods 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 23
- 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 claims 7
- 230000015556 catabolic process Effects 0.000 claims 2
- 238000006731 degradation reaction Methods 0.000 claims 2
- 238000005303 weighing Methods 0.000 claims 2
- 229910052724 xenon Inorganic materials 0.000 claims 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims 2
- 238000003795 desorption Methods 0.000 claims 1
- 238000000695 excitation spectrum Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002073 nanorod Substances 0.000 claims 1
- 238000011056 performance test Methods 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 238000004611 spectroscopical analysis Methods 0.000 claims 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
Abstract
本发明公开了在可见光照射下具有优异光催化性能的棒状铈掺杂氧化锌与石墨烯复合材料光催化剂的制备方法与流程,属于材料制备技术领域,实验采用一步水热法依次合成了氧化锌、不同掺杂浓度的铈掺杂氧化锌与石墨烯复合材料光催化剂粉体,探究了最佳掺比浓度(掺铈质量比为2%)并对样品进行了测试与表征。本发明的特点是:光催化剂制备方法简单,高催化效率,成本低,产率高,无污染。
Description
技术领域
本发明属于材料制备领域,涉及镧系元素铈掺杂N型半导体氧化锌与石墨烯复合材料的制备及其光催化性能的研究,研究了铈掺杂氧化锌与石墨烯复合材料和纯氧化锌光催化性能的差异,并探究了铈的掺比浓度对光催化性能的影响。
背景技术
作为最具前景的光催化基础材料,氧化锌(ZnO)具有无毒、无臭、无味、成本低和制备工艺简单等优势,同时,由于其较宽的带隙(3.37eV)和较大的激发结合能(60meV),使其在催化剂、气敏元件、压敏器件、电池、表面声波器件、量子自选电子器件、发光二极管等领域具有巨大潜力。然而,由于ZnO光生电子-空穴对重组率高、可见光区的吸收能力差等自身缺陷,导致了其光催化性能达不到预期效果,大大降低了在光催化领域的利用率。因此需要拓宽ZnO的光响应范围,提高光生电子空穴对的分离效率是改善氧化锌光催化性能的途径。目前,为提高ZnO光催化活性,主要有金属离子掺杂、贵金属复合、半导体复合等方式。掺杂可以在价带和导带之间引入新的中间能级以降低吸收能。此外,掺杂还可以影响ZnO的晶粒尺寸、结晶度、光电性能。在众多掺杂元素中,铈元素被认为是一种理想的掺杂剂,有助于提高氧化锌的光催化活性。铈离子掺杂氧化锌得到了广泛的研究并取得了很大的进展。参阅Chemical Engineering Journal: Highly efficient photocatalyst based on Cedoped ZnO nanorods: Controllable synthesis and enhanced photocatalyticactivity. 第229期第225-233页,参阅Powder Technology : Sonochemically generatedcerium doped ZnO nanorods for highly efficient photocatalytic dyedegradation. 第318期第120-127页。复合材料是弥补单一材料性能缺陷、增强材料性能、混合各种材料性能的重要手段。石墨烯是由碳原子组成的二维蜂窝状网状物,其具有大的比表面积、高的热稳定性和化学稳定性、优良的导电性和迁移率和显著的结构柔韧性。石墨烯在光催化过程中提供具有高电子传导性的网络,并且用作支持材料作为催化剂的载体。氧化锌与石墨烯的协同作用有望改善氧化锌在光催化中的缺陷,从而提高光吸收强度,拓宽光响应范围,抑制载流子复合,提高表面活性,提高光催化活性。参阅SCIENCE :Graphene_ Status and Prospects, 第324期第1530-1534页。参阅EnvironmentalScience and Pollution Research: Synthesis and characterization of Ag/Bi2WO6/GOcomposite for the fast degradation of tylosin under visible light, 第25期第11754-11766页。参阅The Journal of Physical Chemistry C: Controlled Synthesisof CeO2/Graphene Nanocomposites with Highly Enhanced Optical and CatalyticProperties, 第116期第11741-11745页。
发明内容
本发明的目的是在相同实验条件的前提下,制备出氧化锌(ZnO)、氧化锌石墨烯复合材料(ZG)、铈掺杂氧化锌与石墨烯复合材料(ZGCeO1、ZGCeO2、ZGCeO3、ZGCeO4),探究了铈的最佳掺比浓度(掺铈质量比为2%)并探究了掺杂和复合对纯氧化锌光催化性能的影响。
本发明是通过以下工艺过程实现的,本实验所用氧化石墨烯为商用氧化石墨烯,锌源为六水合硝酸锌(Zn(NO3)2•6H2O),铈源为六水合硝酸铈(Ce(NO3)3•6H2O),碱源为氨水(NH3•H2O)和氢氧化钠(NaOH),洗涤剂为去离子水和无水乙醇(C2H5OH),所有材料均为分析纯,无进一步提纯处理。采用一步低温水热法制备了催化剂前驱体。首先,在含有25ml去离子水的烧杯中加入0.524g的Zn(NO3)2•6H2O。持续搅拌30分钟,逐滴加入氨水将溶液的pH值调至11后再持续搅拌1小时(溶液A),后装入密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10小时,将所得产物用去离子水和无水乙醇洗涤数次,将杂质洗涤出并离心,得到白色产物在70℃下真空干燥10h。所得产物为ZnO样品。重复溶液A的制备过程,另取一装有25ml去离子水的烧杯中加入0.1125g氧化石墨烯超声30分钟,后逐滴加入NaOH溶液将氧化石墨烯溶液的pH值调至4,持续搅拌1小时(溶液B),将搅拌完成的溶液A和B混合,搅拌30分钟,后将溶液转移到密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10h,反应后的溶液用去离子水和无水乙醇多次洗涤,得到的产物在70℃下真空干燥10h。所得产物为ZG样品。称取0.524g的Zn(NO3)2•6H2O加入到装有25ml去离子水的烧杯中,称取0.0059g(1wt%)的Ce(NO3)3•6H2O倒入上述烧杯中,持续搅拌30分钟,然后在两种溶液中加入NaOH,使pH值提高到11,搅拌30分钟,逐滴加入氨水将溶液的pH值调至11后再持续搅拌1小时(溶液C)。在此期间称取0.1125g氧化石墨烯倒入装有25ml去离子水的烧杯中,超声30分钟,后逐滴加入NaOH溶液将氧化石墨烯溶液的pH值调至4,持续搅拌1小时(溶液D),将搅拌完成的溶液C和D混合,搅拌30分钟,后将溶液转移到密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10h,反应后的溶液用去离子水和无水乙醇多次洗涤,得到的产物在70℃下真空干燥10h。所得产物为ZGCeO1样品。ZGCeO2(2wt%),ZGCeO3(3wt%)和ZGCeO4(4wt%)样品用同样实验方法制得。用上述方法共制得ZnO,ZG,ZGCeO1,ZGCeO2,ZGCeO3和ZGCeO4在内的6钟样品并进行进一步表征。
本发明所制得的氧化锌(ZnO)、氧化锌石墨烯复合材料(ZG)、铈掺杂氧化锌与石墨烯复合材料(ZGCeO1、ZGCeO2、ZGCeO3、ZGCeO4)的X-射线衍射光谱图(XRD)如图1所示,纯ZnO和ZGCeO2样品的扫描电子显微图像(SEM)如图2所示,ZGCeO2样品的元素映射图(Mapping)如图3所示,所有样品的紫外-可见光吸收光谱(UV-Vis)及对应的Tauc图如图4所示,所有样品的光致发光光谱图(PL)如图5所示,空白组,ZnO和ZGCeO2光照80分钟亚甲基蓝(MB)的吸光度图谱以及所有样品的光催化活性测试如图6所示。本发明的特点在于:用简单的一步水热法制备了含氧化锌(ZnO)、氧化锌石墨烯复合材料(ZG)、铈掺杂氧化锌与石墨烯复合材料(ZGCeO1、ZGCeO2、ZGCeO3、ZGCeO4)在内的6种光催化剂,通过调节pH值使其均在同一碱性环境下生长,长出的形貌均为六方棒状,目标产物(ZGCeO2)的光的吸收增强,光响应范围拓宽,电子空穴对的分离效率明显增强,电子跃迁回到基态的电子减少,光生载流子被有效分离,光催化活性大大提高。
附图说明
图1为氧化锌(ZnO)、氧化锌石墨烯复合材料(ZG)、铈掺杂氧化锌与石墨烯复合材料(ZGCeO1、ZGCeO2、ZGCeO3、ZGCeO4)的X-射线衍射光谱图,其中图a为衍射角为20°-80°的XRD总图谱,图b为放大(101)面的衍射峰图谱。
图2为纯ZnO 和ZGCeO2样品的扫描电子显微图像(SEM),其中图a,b分别对应为纯ZnO,ZGCeO2的显微图片,图c为ZGCeO2微观结构示意图。
图3为ZGCeO2样品的元素映射图(Mapping),其中,图a,b,c,d分别为样品ZGCeO2的C,O,Zn,Ce元素的Mapping图。
图4为所有样品的紫外-可见光吸收光谱(UV-Vis)(图a)及对应的Tauc图(图b)。
图5为所有样品的光致发光光谱图(PL)。
图6为空白组,ZnO和ZGCeO2光照80分钟亚甲基蓝(MB)的吸光度图谱以及所有样品的光催化活性测试图,其中图a-c分别为空白组,ZnO和ZGCeO2光照80分钟亚甲基蓝(MB)的吸光度图谱;d为不同掺杂浓度的光催化剂对MB的光降解曲线;e为MB光降解动力学曲线;f为不同掺杂浓度的光催化剂的速率常数柱状图。
具体实施方式
实施例1
首先,在含有25ml去离子水的烧杯中加入0.524g的Zn(NO3)2•6H2O。持续搅拌30分钟,逐滴加入氨水将溶液的pH值调至11后再持续搅拌1小时(溶液A),后装入密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10小时,将所得产物用去离子水和无水乙醇洗涤数次,将杂质洗涤出并离心,得到白色产物在70℃下真空干燥10h。所得产物为ZnO样品。
实施例2
重复溶液A的制备过程,另取一装有25ml去离子水的烧杯中加入0.1125g氧化石墨烯超声30分钟,后逐滴加入NaOH溶液将氧化石墨烯溶液的pH值调至4,持续搅拌1小时(溶液B),将搅拌完成的溶液A和B混合,搅拌30分钟,后将溶液转移到密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10h,反应后的溶液用去离子水和无水乙醇多次洗涤,得到的产物在70℃下真空干燥10h。所得产物为ZG样品。
实施例3
称取0.524g的Zn(NO3)2•6H2O加入到装有25ml去离子水的烧杯中,称取0.0059g(1wt%)的Ce(NO3)3•6H2O倒入上述烧杯中,持续搅拌30分钟,然后在两种溶液中加入NaOH,使pH值提高到11,搅拌30分钟,逐滴加入氨水将溶液的pH值调至11后再持续搅拌1小时(溶液C)。在此期间称取0.1125g氧化石墨烯倒入装有25ml去离子水的烧杯中,超声30分钟,后逐滴加入NaOH溶液将氧化石墨烯溶液的pH值调至4,持续搅拌1小时(溶液D),将搅拌完成的溶液C和D混合,搅拌30分钟,后将溶液转移到密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10h,反应后的溶液用去离子水和无水乙醇多次洗涤,得到的产物在70℃下真空干燥10h。所得产物为ZGCeO1样品。ZGCeO2(2wt%),ZGCeO3(3wt%)和ZGCeO4(4wt%)样品用同样实验方法制得。
Claims (4)
1.一种在可见光照射下具有优异光催化性能的棒状铈掺杂氧化锌与石墨烯复合材料光催化剂,其特征为低成本,无污染,高催化效率,制备方法简单;本实验所用氧化石墨烯为商用氧化石墨烯,锌源为六水合硝酸锌(Zn(NO3)2•6H2O),铈源为六水合硝酸铈(Ce(NO3)3•6H2O),碱源为氨水(NH3•H2O)和氢氧化钠(NaOH),洗涤剂为去离子水和无水乙醇(C2H5OH),所有材料均为分析纯,无进一步提纯处理;采用一步低温水热法制备了催化剂前驱体,首先,在含有25ml去离子水的烧杯中加入0.524g的Zn(NO3)2•6H2O;持续搅拌30分钟,逐滴加入氨水将溶液的pH值调至11后再持续搅拌1小时(溶液A),后装入密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10小时,将所得产物用去离子水和无水乙醇洗涤数次,将杂质洗涤出并离心,得到白色产物在70℃下真空干燥10h,所得产物为ZnO样品;重复溶液A的制备过程,另取一装有25ml去离子水的烧杯中加入0.1125g氧化石墨烯超声30分钟,后逐滴加入NaOH溶液将氧化石墨烯溶液的pH值调至4,持续搅拌1小时(溶液B),将搅拌完成的溶液A和B混合,搅拌30分钟,后将溶液转移到密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10h,反应后的溶液用去离子水和无水乙醇多次洗涤,得到的产物在70℃下真空干燥10h,所得产物为ZG样品;称取0.524g的Zn(NO3)2•6H2O加入到装有25ml去离子水的烧杯中,称取0.0059g(1wt%)的Ce(NO3)3•6H2O倒入上述烧杯中,持续搅拌30分钟,然后在两种溶液中加入NaOH,使pH值提高到11,搅拌30分钟,逐滴加入氨水将溶液的pH值调至11后再持续搅拌1小时(溶液C);在此期间称取0.1125g氧化石墨烯倒入装有25ml去离子水的烧杯中,超声30分钟,后逐滴加入NaOH溶液将氧化石墨烯溶液的pH值调至4,持续搅拌1小时(溶液D),将搅拌完成的溶液C和D混合,搅拌30分钟,后将溶液转移到密封的聚四氟乙烯衬里的不锈钢高压釜中,180℃反应10h,反应后的溶液用去离子水和无水乙醇多次洗涤,得到的产物在70℃下真空干燥10h,所得产物为ZGCeO1样品;ZGCeO2(2wt%),ZGCeO3(3wt%)和ZGCeO4(4wt%)样品用同样实验方法制得;用上述方法共制得ZnO,ZG,ZGCeO1,ZGCeO2,ZGCeO3和ZGCeO4在内的6钟样品,通过一系列的表征手段如X射线衍射(XRD)、扫描电子显微镜(SEM)、元素映射图(Mapping)、紫外-可见光吸收谱(UV-Vis)、荧光激发光谱(PL)来分析样品的形貌、结构、成分和光学性质,光催化性能测试我们使用的光源是350w氙灯,降解的目标染料是亚甲基蓝(MB);有机染料浓度为10mg/L,持续搅拌3小时;称取30mg样品放入装有50ml有机染料的四个试管中搅拌,使催化剂和染料充分接触;暗处理30分钟后有机染料与光催化剂达到吸附和解吸的平衡;之后,打开氙灯,每30分钟取出3-4ml溶液;用紫外-可见光谱法测定MB在664nm处的吸收峰,根据降解率a=((C0-C)/C0)*100%(MB的初始吸光度值设为C0,降解后MB的吸光度值设为C)计算MB的降解率,以亚甲基蓝溶液吸光度的变化来评估样品的光催化性能;根据光催化结果,发现ZGCeO2(2wt%)样品显示出最高的光催化活性。
2.如权利要求1所示,其特征在于,水热合成时氧化石墨烯pH值调节为4,金属盐溶液pH值调节为11,温度为180℃下水热反应10小时可制备得到氧化锌纳米棒。
3.如权利要求1所示,其特征在于,目标产物中铈所占的质量比为2%。
4.如权利要求1所示,其特征在于,石墨烯所占的质量比为23.8%。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010040052.7A CN111644170A (zh) | 2020-01-15 | 2020-01-15 | 一种在可见光照射下具有优异光催化性能的棒状铈掺杂氧化锌与石墨烯复合材料光催化剂 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010040052.7A CN111644170A (zh) | 2020-01-15 | 2020-01-15 | 一种在可见光照射下具有优异光催化性能的棒状铈掺杂氧化锌与石墨烯复合材料光催化剂 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111644170A true CN111644170A (zh) | 2020-09-11 |
Family
ID=72348427
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010040052.7A Pending CN111644170A (zh) | 2020-01-15 | 2020-01-15 | 一种在可见光照射下具有优异光催化性能的棒状铈掺杂氧化锌与石墨烯复合材料光催化剂 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111644170A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112642426A (zh) * | 2020-12-23 | 2021-04-13 | 上海聚治新材料科技有限公司 | 一种贵金属/石墨烯担载锰锌基弱光光触媒的制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103143371A (zh) * | 2013-03-18 | 2013-06-12 | 新疆大学 | 一种异质结构硫化锌光催化剂的固相制备 |
US20150031141A1 (en) * | 2013-07-24 | 2015-01-29 | Umm Al-Qura University | Composition and method of using a catalyst for photo-catalytic degradation of contaminant in water |
CN106268953A (zh) * | 2016-08-12 | 2017-01-04 | 桂林电子科技大学 | 一种氧化石墨烯和含铈配位聚合物的棒状多孔复合材料及其制备方法 |
CN107107052A (zh) * | 2015-11-11 | 2017-08-29 | 沙特基础工业全球技术公司 | 含有纳米碳和纳米结构或微米结构和经煅烧的水滑石壳的多功能稳定纳米构造体 |
CN108906025A (zh) * | 2018-08-01 | 2018-11-30 | 安徽锦华氧化锌有限公司 | 一种稀土元素掺杂改性纳米氧化锌-石墨烯复合光催化材料的制备方法 |
CN110538649A (zh) * | 2019-09-17 | 2019-12-06 | 新疆大学 | 一种在可见光照射下具有优异光催化性能的氧化锌基复合光催化剂 |
US20210252486A1 (en) * | 2018-06-22 | 2021-08-19 | The Curators Of The University Of Missouri | Novel method of manufacture of metal nanoparticles and metal single-atom materials on various substrates and novel compositions |
-
2020
- 2020-01-15 CN CN202010040052.7A patent/CN111644170A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103143371A (zh) * | 2013-03-18 | 2013-06-12 | 新疆大学 | 一种异质结构硫化锌光催化剂的固相制备 |
US20150031141A1 (en) * | 2013-07-24 | 2015-01-29 | Umm Al-Qura University | Composition and method of using a catalyst for photo-catalytic degradation of contaminant in water |
CN107107052A (zh) * | 2015-11-11 | 2017-08-29 | 沙特基础工业全球技术公司 | 含有纳米碳和纳米结构或微米结构和经煅烧的水滑石壳的多功能稳定纳米构造体 |
CN106268953A (zh) * | 2016-08-12 | 2017-01-04 | 桂林电子科技大学 | 一种氧化石墨烯和含铈配位聚合物的棒状多孔复合材料及其制备方法 |
US20210252486A1 (en) * | 2018-06-22 | 2021-08-19 | The Curators Of The University Of Missouri | Novel method of manufacture of metal nanoparticles and metal single-atom materials on various substrates and novel compositions |
CN108906025A (zh) * | 2018-08-01 | 2018-11-30 | 安徽锦华氧化锌有限公司 | 一种稀土元素掺杂改性纳米氧化锌-石墨烯复合光催化材料的制备方法 |
CN110538649A (zh) * | 2019-09-17 | 2019-12-06 | 新疆大学 | 一种在可见光照射下具有优异光催化性能的氧化锌基复合光催化剂 |
Non-Patent Citations (1)
Title |
---|
YA NAN WANG ET AL.,: ""The performance of daylight photocatalytic activity towards degradation of MB by the flower-like and approximate flower-like complexes of graphene with ZnO and Cerium doped ZnO"", 《OPTIK》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112642426A (zh) * | 2020-12-23 | 2021-04-13 | 上海聚治新材料科技有限公司 | 一种贵金属/石墨烯担载锰锌基弱光光触媒的制备方法 |
CN112642426B (zh) * | 2020-12-23 | 2023-09-12 | 上海聚治新材料科技有限公司 | 一种贵金属/石墨烯担载锰锌基弱光光触媒的制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Jin et al. | Ni, Co-based selenide anchored g-C3N4 for boosting photocatalytic hydrogen evolution | |
Liu et al. | Peroxymonosulfate-assisted for facilitating photocatalytic degradation performance of 2D/2D WO3/BiOBr S-scheme heterojunction | |
Huang et al. | Noble metal-free MoS2 modified Mn0. 25Cd0. 75S for highly efficient visible-light driven photocatalytic H2 evolution | |
Chen et al. | Hollow ZnCdS dodecahedral cages for highly efficient visible-light-driven hydrogen generation | |
Wang et al. | MoS 2/CQDs obtained by photoreduction for assembly of a ternary MoS 2/CQDs/ZnIn 2 S 4 nanocomposite for efficient photocatalytic hydrogen evolution under visible light | |
Ao et al. | Fabrication of novel p–n heterojunction BiOI/La 2 Ti 2 O 7 composite photocatalysts for enhanced photocatalytic performance under visible light irradiation | |
Liu et al. | Charge transmission channel construction between a MOF and rGO by means of Co–Mo–S modification | |
CN107376944B (zh) | 过渡金属硫化物负载Mn-Cd-S固溶体在光催化产氢方面的应用 | |
Xin et al. | Synthesis of ZnS@ CdS–Te composites with p–n heterostructures for enhanced photocatalytic hydrogen production by microwave-assisted hydrothermal method | |
Yang et al. | Self-assembly Z-scheme heterostructured photocatalyst of Ag 2 O@ Ag-modified bismuth vanadate for efficient photocatalytic degradation of single and dual organic pollutants under visible light irradiation | |
CN108404959B (zh) | 一种棒状g-C3N4@SnIn4S8复合光催化剂及其制备方法 | |
CN108786849B (zh) | 一种硫化锡/二氧化钛复合材料的制备和应用 | |
CN110721698B (zh) | 一种钒酸铋/钒酸铜复合光催化剂及其制备方法和应用 | |
Wang et al. | Rose spherical structure Ag2S/ZnIn2S4/ZnS composites with visible light response: enhanced photodegradation and hydrogen production performance | |
CN113145138A (zh) | 热响应型复合光催化剂及其制备方法和应用 | |
CN111644192A (zh) | 一种g-C3N4@CdxZn1-xSe复合光催化剂及其制备方法和应用 | |
Li et al. | The hydrothermal synthesis of ZnSn (OH) 6 and Zn 2 SnO 4 and their photocatalytic performances | |
Zhong et al. | Plasma-induced black bismuth tungstate as a photon harvester for photocatalytic carbon dioxide conversion | |
CN103521244B (zh) | 一种光催化分解水制氢材料CdS/Sr1.6Zn0.4Nb2O7及其制备方法 | |
Kao et al. | MoS2-coupled coniferous ZnO for photocatalytic degradation of dyes | |
CN109382088B (zh) | SnO2/α~Bi2O3/β~Bi2O3复合材料及其制备方法 | |
Zhou et al. | Highly efficient solar-driven photocatalytic hydrogen evolution by a ternary 3D ZnIn 2 S 4–MoS 2 microsphere/1D TiO 2 nanobelt heterostructure | |
Li et al. | A simple synthetic strategy toward recyclable polyurethane foam supported defective CoFeAl-layered double hydroxides for antibiotics photocatalytic degradation | |
Zhao et al. | A hollow core–shell structure material NiCo 2 S 4@ Ni 2 P with uniform heterojunction for efficient photocatalytic H 2 evolution reaction | |
Zou et al. | Inorganic anions assisted on crystal transition of polymorphic ZnIn2S4 for enhanced photocatalytic tetracycline hydrochloride degradation and Cr (VI) reduction |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200911 |
|
WD01 | Invention patent application deemed withdrawn after publication |