CN111514892A - 一种钒酸铋/铬酸银异质结光催化剂及其制备方法和应用 - Google Patents
一种钒酸铋/铬酸银异质结光催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN111514892A CN111514892A CN202010429241.3A CN202010429241A CN111514892A CN 111514892 A CN111514892 A CN 111514892A CN 202010429241 A CN202010429241 A CN 202010429241A CN 111514892 A CN111514892 A CN 111514892A
- Authority
- CN
- China
- Prior art keywords
- bivo
- solution
- heterojunction photocatalyst
- bismuth vanadate
- heterojunction
- 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.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 63
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 53
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 53
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000011449 brick Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 35
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000001016 thiazine dye Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 15
- 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 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 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
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/685—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with chromium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明公开一种钒酸铋/铬酸银异质结光催化剂及其制备方法和应用:该异质结光催化剂由BiVO4及选择性沉积在BiVO4(040)晶面上的纳米Ag2CrO4组装而成,所述BiVO4具有切角的四方双锥体微观结构,且BiVO4质量占所述异质结光催化剂总质量的70~80%;包括以下步骤:S1:水热法制备钒酸铋;S2:制备异质结光催化剂:将BiVO4加入蒸馏水中,超声分散后,在磁力搅拌的条件下,加入一定量的AgNO3溶液后,再缓慢滴加一定量的K2CrO4溶液,生成砖红色沉淀,并持续搅拌反应1~2h,再静置沉淀陈化12~24h,离心,水洗6次,真空干燥。相比于传统沉积方法,本发明选择性吸附沉积的方法形成的异质结稳定性更好,界面结合度更高,具有较高的可见光催化活性。
Description
技术领域
本发明属于光催化技术领域,涉及一种钒酸铋/铬酸银异质结光催化剂的制备方法,特别涉及一种铬酸银修饰的钒酸铋复合光催化剂,主要用于复合光催化剂在可见光催化降解有机染料中的应用。
背景技术
钒酸铋作为一种非TiO2基可见光半导体催化剂,禁带宽度(单斜相)2.4eV,无毒,价廉,色泽好,同时还具有很多优异的物理化学性质,因而在光催化领域引起了广泛的关注。尽管钒酸铋有较好的可见光吸收特性,但仍存在表面吸附能力弱,光生空穴和电子易于复合等问题,导致实际的量子效率不高。
为了提高光催化反应的量子效率,科研人员采取不同的方法和手段对钒酸铋进行改性,主要包括非金属元素掺杂、贵金属沉积、半导体形貌控制合成以及形成复合物异质结。研究表明,在钒酸铋表面沉积贵金属纳米颗粒可以抑制光生电子-空穴的复合,显著提高钒酸铋的光催化活性。通过元素的掺杂,不仅可以提高钒酸铋对可见光的吸收,而且可以有效的捕获光生电子和空穴,抑制了光生载流子的复合,提高了光催化的效率。除此之外,构造半导体异质结是提高钒酸铋光生载流子分离效率的另一种有效途径。将两种晶格匹配的半导体材料依靠某种强相互作用复合在一起,在接触处会形成明显的界面,界面电场的驱动能够使光生载流子有效分离。
尽管通过贵金属沉积、元素掺杂、构建异质结等手段大大提高了钒酸铋的光催化活性,但还是存在诸多的问题。例如沉积贵金属将会增加催化剂的成本,常规方法所制备的异质结质量差(如结合不牢固、均匀性差)等。因此,开发简单、制备价格低廉、高质量、高活性的可见光催化剂仍是重要的研究方向。
发明内容
针对现有技术的不足之处,本发明的目的在于一种钒酸铋/铬酸银异质结光催化剂及其制备方法和应用。
本发明的技术方案概述如下:
一种钒酸铋/铬酸银异质结光催化剂:该异质结光催化剂由BiVO4及选择性沉积在BiVO4(040)晶面上的纳米Ag2CrO4组装而成,所述BiVO4具有切角的四方双锥体微观结构,且BiVO4质量占所述异质结光催化剂总质量的70~80%。
一种钒酸铋/铬酸银异质结光催化剂的制备方法,包括以下步骤:
S1:水热法制备钒酸铋:向Bi(NO3)3-HNO3溶液中逐滴滴加十二烷基磺酸钠水溶液,混合均匀后,在剧烈搅拌的条件下,缓慢加入NH4VO3-NH3·H2O溶液,控制Bi3+、VO3 +、十二烷基磺酸钠用量比例为5mmol:5mmol:1g,搅拌0.5h,再调节pH至7.0,继续搅拌2h后,将反应溶液转移到高压反应釜,再于120~200℃水热晶化18~32h,冷却、离心,分别用乙醇和高纯水洗涤下层沉淀物2~3次,80℃真空干燥12h,即得BiVO4;
S2:制备异质结光催化剂:将BiVO4加入蒸馏水中,超声分散后,在磁力搅拌的条件下,加入一定量的AgNO3溶液后,并继续搅拌10~15h,再缓慢滴加一定量的K2CrO4溶液,生成砖红色沉淀,并持续搅拌反应1~2h,再静置沉淀陈化3~5h,离心,水洗下层沉淀物6次,80℃真空干燥6h,得到BiVO4质量分数为70~80%的异质结光催化剂。
优选的是,所述Bi(NO3)3-HNO3溶液制备方法为:称取2.5mmol Bi(NO3)3·5H2O,加入50mL的2mol/L稀硝酸溶液,搅拌0.5h使其完全溶解。
优选的是,所述NH4VO3-NH3·H2O溶液制备方法为:称取2.5mmol NH4VO3,加入50mL的1mol/L氨水溶液,搅拌0.5h使其完全溶解。
优选的是,所述离心转速为4500r/min。
一种钒酸铋/铬酸银异质结光催化剂在降解噻嗪染料废水中的应用。
本发明的有益效果:
1、本发明通过两步法进行制备出钒酸铋/铬酸银异质结光催化剂,先水热法合成出暴露BiVO4(040)晶面的切角四方双锥体钒酸铋,再选择性沉积铬酸银纳米颗粒。十二烷基磺酸钠(SDS)作为结构导向剂,覆盖于在大多数BiVO4的晶面,只有BiVO4的(040)晶面没有被SDS覆盖,在高能的BiVO4(040)晶面上,大量的悬挂键被优先暴露出来,为Ag+提供了充足的吸附位,因而Ag+被选择性吸附在BiVO4(040)晶面,Ag+进一步与CrO4 2-作用生成微小的铬酸银晶种,并逐渐生长成均一、稳定的铬酸银纳米颗粒,相比于传统沉积方法,本发明吸附沉积的方法形成的异质结稳定性更好,界面结合度更高。
2、本发明钒酸铋/铬酸银异质结光催化剂在可见光激发下,产生的光生电子与空穴在异质结界面向不同方向转移,光生电子自发由铬酸银纳米颗粒转移到钒酸铋的(040)晶面,而空穴则分布于铬酸银纳米颗粒表面及钒酸铋的其他晶面,实现了电子与空穴的有效分离,减少电子-空穴对数量,进而大大提高了光催化活性和稳定性;同时,铬酸银的禁带宽度较窄,有效扩大光催化剂对可见光的响应波长范围,进而提高其对可见光的利用率,增强光催化活性。
附图说明
图1为实施例2及对照组制备出的光催化剂样品X射线衍射(XRD)图谱;
图2为实施例2制备的BiVO4(其含量为80%)/Ag2CrO4异质结光催化剂的扫描电子显微镜(SEM)图;
图3为实施例2及对照组制备出的光催化剂紫外-可见漫反射(DRS)光谱图;
图4为实施例2及对照组制备出的光催化剂红外光谱图;
图5为实施例1~2及对照组1~3制备出的光催化剂降解10mg/L亚甲基蓝的趋势图;
图6为本发明BiVO4/Ag2CrO4异质结光催化剂的制备方法流程图。
图1、3、4中,(a)为对照组1BiVO4;(b)为对照组2制备的Ag2CrO4;(c)为实施例2制备的BiVO4(其含量为80%)/Ag2CrO4异质结光催化剂。
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。
实施例1
一种钒酸铋/铬酸银异质结光催化剂的制备方法,包括以下步骤:
S1:水热法制备钒酸铋:
a.取2.5mmol Bi(NO3)3·5H2O加到50mL的2mol/L稀硝酸溶液/取2.5mmol NH4VO3加到50mL的2mol/L氨水溶液中,搅拌0.5h促进其完全溶解,得到澄清透明的Bi(NO3)3-HNO3/NH4VO3-NH3·H2O溶液;取0.5g十二烷基磺酸钠(SDS),加入到20mL高纯水中,搅拌促进其完全溶解,得到SDS水溶液;
b.向Bi(NO3)3-HNO3溶液中逐滴滴加SDS水溶液,混合均匀后,在剧烈搅拌的条件下,缓慢加入NH4VO3-NH3·H2O溶液,搅拌0.5h,再用2mol/L氨水溶液调节pH至7.0,继续搅拌2h后,将反应溶液转移到高压反应釜,再于180℃水热晶化24h,自然冷却至室温,以4500r/min转速离心分离后,分别用乙醇和高纯水洗涤下层沉淀物3次,除去残留的离子及表面的有机物,80℃真空干燥12h,即得样品BiVO4;
S2:制备异质结光催化剂:
a.准确称取的0.5g BiVO4、0.1311g AgNO3和0.0750g K2CrO4,将AgNO3、K2CrO4分别配成100mL的溶液;
b.将称取好的0.5g BiVO4加入100mL蒸馏水中,超声分散后,在磁力搅拌的条件下,加入100mL AgNO3溶液后,并继续搅拌12h,再缓慢滴加100mL K2CrO4溶液,生成砖红色沉淀,并持续搅拌反应1,再静置沉淀陈化4h,以4500r/min转速离心使其与水分离,并水洗下层沉淀物6次以除去未反应的试剂和杂质,80℃真空干燥6h,得到BiVO4质量分数为70%的BiVO4/Ag2CrO4异质结光催化剂样品。
实施例2
一种钒酸铋/铬酸银异质结光催化剂的制备方法,包括以下步骤:
S1:水热法制备钒酸铋:同实施例1;
S2:制备异质结光催化剂:
a.准确称取的0.5g BiVO4、0.2248g AgNO3和0.1285g K2CrO4,将AgNO3、K2CrO4分别配成100mL的溶液;
b.将称取好的0.5g BiVO4加入100mL蒸馏水中,超声分散后,在磁力搅拌的条件下,加入100mL AgNO3溶液后,并继续搅拌12h,再缓慢滴加100mL K2CrO4溶液,生成砖红色沉淀,并持续搅拌反应1,再静置沉淀陈化4h,以4500r/min转速离心使其与水分离,并水洗下层沉淀物6次以除去未反应的试剂和杂质,80℃真空干燥6h,得到BiVO4质量分数为80%的BiVO4/Ag2CrO4异质结光催化剂样品。
对照组1为实施例2中剩余BiVO4,对照组2为Ag2CrO4,对照组3为BiVO4质量分数为90%的BiVO4/Ag2CrO4异质结光催化剂。
对照组2制备方法:配制1000mL的0.5mol/LAgNO3水溶液和1000mL的0.25mol/LK2CrO4水溶液;在剧烈搅拌条件下,将AgNO3水溶液倒入K2CrO4水溶液中混合在一起,持续搅拌1h,然后陈化24h后,以4500r/min转速离心,并水洗下层沉淀物6次以除去未反应的试剂和杂质,80℃真空干燥6h,得到样品Ag2CrO4。
对照组3制备方法:
S1:水热法制备钒酸铋:同实施例1;
S2:制备异质结光催化剂:
a.准确称取的0.5g BiVO4、0.0583g AgNO3和0.0333g K2CrO4,将AgNO3、K2CrO4分别配成100mL的溶液;
b.将称取好的0.5g BiVO4加入100mL蒸馏水中,超声分散后,在磁力搅拌的条件下,加入100mL AgNO3溶液后,并继续搅拌12h,再缓慢滴加100mL K2CrO4溶液,生成砖红色沉淀,并持续搅拌反应1,再静置沉淀陈化4h,以4500r/min转速离心使其与水分离,并水洗下层沉淀物6次以除去未反应的试剂和杂质,80℃真空干燥6h,得到BiVO4质量分数为90%的BiVO4/Ag2CrO4异质结光催化剂样品。
图1为实施例2及对照组制备出的光催化剂样品X射线衍射(XRD)图谱,(a)为对照组1BiVO4;(b)为对照组2制备的Ag2CrO4;(c)为实施例2制备的BiVO4(其含量为80%)/Ag2CrO4异质结光催化剂:通过XRD表征可以看出,实施例2所制备的钒酸铋前驱体在18.98°,28.95°,30.55°,34.56°,35.32°,40.25°,42.46°,46.13°,46.60°,47.31°,50.31°,53.01°,58.29°,59.58°等衍射角的位置上具有的特征峰,分别为单斜相白钨矿型钒酸铋(011),(121),(040),(200),(002),(112),(051),(132),(240),(042),(202),(161),(321),(123)晶面的吸收峰,且无其他杂质峰,说明制备的钒酸铋前驱体为单斜相白钨矿型。复合物特征峰的位置和峰形相对于纯的钒酸铋来说基本上没有发生改变,表明铬酸银的复合并不影响钒酸铋的晶格结构。实施例2异质结光催化剂中,BiVO4(040)晶面衍射强度相比(121)晶面衍射强度为0.41,而纯钒酸铋中(040)晶面衍射强度相比(121)晶面衍射强度为0.53,即(040)晶面衍射峰强度变弱,这说明铬酸银的选择性沉积覆盖了钒酸铋的(040)晶面,铬酸银的沉积具有晶面选择性,也进一步说明成功合成了铬酸银和钒酸铋两种半导体的复合材料。
图2为实施例2制备的BiVO4(其含量为80%)/Ag2CrO4异质结光催化剂的扫描电子显微镜(SEM)图:通过SEM来表征铬酸银和钒酸铋的接触情况,由图2可以看出铬酸银和钒酸铋之间精密接触,形成明显的相界面,说明两者之间形成了高质量的异质结结构,这对电荷在两种半导体之间的转移具有非常重要的作用。
图3为实施例2及对照组制备出的光催化剂紫外-可见漫反射(DRS)光谱图,(a)为对照组1BiVO4;(b)为对照组2制备的Ag2CrO4;(c)为实施例2制备的BiVO4(其含量为80%)/Ag2CrO4异质结光催化剂:由图3可以看出,纯钒酸铋的吸收边位于530nm左右,而铬酸银的吸收边可达700nm左右,可见钒酸铋和铬酸银都具有很好的可见光响应性能,都可以被用作良好的可见光光催化剂,而得到的异质结光催化剂的吸收边在500-700nm的范围内,具有一定的光吸收性能。
图4为实施例2及对照组制备出的光催化剂红外光谱图,(a)为对照组1BiVO4;(b)为对照组2制备的Ag2CrO4;(c)为实施例2制备的BiVO4(其含量为80%)/Ag2CrO4异质结光催化剂:由图4可知,异质结光催化剂中既存在铬酸银的振动峰又存在钒酸铋的特征峰,在500-1000cm-1范围内的振动峰可归属于钒酸铋的V-O键的振动峰,结果表明复合材料既存在铬酸银相又存在钒酸铋相。
测定实施例1~2及对照组1~3催化剂的可见光催化性能:
本发明采用钒酸铋/铬酸银复合光催化剂在可见光下降解亚甲基蓝的方法:降解亚甲基蓝的实验条件为:先在黑暗条件下,依次称取50mg的实施例1~2及对照组1~3催化剂样品,分别加入5组100ml的10mg/L亚甲基蓝溶液中,搅拌均匀后,打开500W氙灯光源,并用可见光滤光片使得420nm以上的可见光通过滤光片,照射到混合悬液中,间隔3分钟进行取样分析,测定降解过程中亚甲基蓝的浓度C,并计算C/C0,C0为10mg/L,绘制图5钒酸铋、铬酸银以及不同含量的钒酸铋/铬酸银异质结催化剂降解10mg/L亚甲基蓝的趋势图。
由图5可知,实施例2制备的BiVO4(其含量为80%)/Ag2CrO4异质结光催化剂对亚甲基蓝MB催化降解速率最快,对太阳能的利用率提高,两者形成异质结的同时加快了光生电子的迁移速率,使光生电子和空穴的复合几率大大降低,同时实施例1制备的BiVO4(其含量为70%)/Ag2CrO4异质结光催化剂和实施例2在第6min时对亚甲基蓝的降解率即可达到90%以上,在第9min时对亚甲基蓝的降解率即可达到95%以上,且降解平衡时达到100%,而对照组3在第6min时对亚甲基蓝的降解率不到70%,在第9min时对亚甲基蓝的降解率约85%,且降解平衡时仅95%附近,说明BiVO4与Ag2CrO4的复合比例也是决定光催化活性的重要因素,BiVO4含量过高时,Ag2CrO4不足以完全沉积BiVO4的(040)晶面,无法实现电子与空穴完全分离的效果,而BiVO4含量过低时,Ag2CrO4在BiVO4的(040)晶面沉积厚度过高,光线无法透射到BiVO4晶面,致使BiVO4的光敏性较差,也会影响光催化活性。
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。
Claims (6)
1.一种钒酸铋/铬酸银异质结光催化剂,其特征在于:该异质结光催化剂由BiVO4及选择性沉积在BiVO4(040)晶面上的纳米Ag2CrO4组装而成,所述BiVO4具有切角的四方双锥体微观结构,且BiVO4质量占所述异质结光催化剂总质量的70~80%。
2.如权利要求1所述一种钒酸铋/铬酸银异质结光催化剂的制备方法,其特征在于,包括以下步骤:
S1:水热法制备钒酸铋:向Bi(NO3)3-HNO3溶液中逐滴滴加十二烷基磺酸钠水溶液,混合均匀后,在剧烈搅拌的条件下,缓慢加入NH4VO3-NH3·H2O溶液,控制Bi3+、VO3 +、十二烷基磺酸钠用量比例为5mmol:5mmol:1g,搅拌0.5h,再调节pH至7.0,继续搅拌2h后,将反应溶液转移到高压反应釜,再于120~200℃水热晶化18~32h,冷却、离心,分别用乙醇和高纯水洗涤下层沉淀物2~3次,80℃真空干燥12h,即得BiVO4;
S2:制备异质结光催化剂:将BiVO4加入蒸馏水中,超声分散后,在磁力搅拌的条件下,加入一定量的AgNO3溶液后,并继续搅拌10~15h,再缓慢滴加一定量的K2CrO4溶液,生成砖红色沉淀,并持续搅拌反应1~2h,再静置沉淀陈化3~5h,离心,水洗下层沉淀物6次,80℃真空干燥6h,得到BiVO4质量分数为70~80%的异质结光催化剂。
3.根据权利要求2所述一种钒酸铋/铬酸银异质结光催化剂的制备方法,其特征在于,所述Bi(NO3)3-HNO3溶液制备方法为:称取2.5mmol Bi(NO3)3·5H2O,加入50mL的2mol/L稀硝酸溶液,搅拌0.5h使其完全溶解。
4.根据权利要求2所述一种钒酸铋/铬酸银异质结光催化剂的制备方法,其特征在于,所述NH4VO3-NH3·H2O溶液制备方法为:称取2.5mmol NH4VO3,加入50mL的2mol/L氨水溶液,搅拌0.5h使其完全溶解。
5.根据权利要求2所述一种钒酸铋/铬酸银异质结光催化剂的制备方法,其特征在于,所述离心转速为4500r/min。
6.如权利要求1~5任一项所述一种钒酸铋/铬酸银异质结光催化剂在降解噻嗪染料废水中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010429241.3A CN111514892B (zh) | 2020-05-20 | 2020-05-20 | 一种钒酸铋/铬酸银异质结光催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010429241.3A CN111514892B (zh) | 2020-05-20 | 2020-05-20 | 一种钒酸铋/铬酸银异质结光催化剂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111514892A true CN111514892A (zh) | 2020-08-11 |
CN111514892B CN111514892B (zh) | 2022-07-08 |
Family
ID=71912423
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010429241.3A Active CN111514892B (zh) | 2020-05-20 | 2020-05-20 | 一种钒酸铋/铬酸银异质结光催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111514892B (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112547063A (zh) * | 2021-01-08 | 2021-03-26 | 上海大学 | 一种Bi2MoO6Ag2CrO4异质结和制备方法及其作为光催化材料的应用 |
CN113477262A (zh) * | 2021-08-09 | 2021-10-08 | 大连工业大学 | 一种铬酸银/铁酸锌纤维状复合光催化剂的制备方法及应用 |
CN113713823A (zh) * | 2021-09-14 | 2021-11-30 | 蚌埠学院 | 一种CoTiO3/BiVO4复合光催化剂的制备方法及应用 |
CN113856671A (zh) * | 2021-08-26 | 2021-12-31 | 浙江工业大学 | 一种含有s空位的z型异质结光催化剂的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106964336A (zh) * | 2017-03-22 | 2017-07-21 | 陕西科技大学 | 一种氧化石墨烯/(040)晶面钒酸铋异质结及其制备方法和应用 |
CN107012474A (zh) * | 2016-01-28 | 2017-08-04 | 中国科学院大连化学物理研究所 | 一种规模化太阳能光催化-光电催化分解水制氢的方法 |
KR101808838B1 (ko) * | 2016-11-28 | 2018-01-18 | 서강대학교산학협력단 | 이산화탄소 광전기화학적 환원 장치 |
CN108940325A (zh) * | 2018-07-23 | 2018-12-07 | 汕头大学 | 一种二元复合半导体光催化剂材料Ag2CrO4/BiOI及其制备与应用 |
CN109133168A (zh) * | 2018-08-06 | 2019-01-04 | 西安电子科技大学 | 一种单斜相截断八面体钒酸铋晶体的制备方法 |
CN110773178A (zh) * | 2019-11-04 | 2020-02-11 | 哈尔滨工业大学 | 一种硅酸银/(040)钒酸铋直接z型光催化剂及其制备方法和应用 |
-
2020
- 2020-05-20 CN CN202010429241.3A patent/CN111514892B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107012474A (zh) * | 2016-01-28 | 2017-08-04 | 中国科学院大连化学物理研究所 | 一种规模化太阳能光催化-光电催化分解水制氢的方法 |
KR101808838B1 (ko) * | 2016-11-28 | 2018-01-18 | 서강대학교산학협력단 | 이산화탄소 광전기화학적 환원 장치 |
CN106964336A (zh) * | 2017-03-22 | 2017-07-21 | 陕西科技大学 | 一种氧化石墨烯/(040)晶面钒酸铋异质结及其制备方法和应用 |
CN108940325A (zh) * | 2018-07-23 | 2018-12-07 | 汕头大学 | 一种二元复合半导体光催化剂材料Ag2CrO4/BiOI及其制备与应用 |
CN109133168A (zh) * | 2018-08-06 | 2019-01-04 | 西安电子科技大学 | 一种单斜相截断八面体钒酸铋晶体的制备方法 |
CN110773178A (zh) * | 2019-11-04 | 2020-02-11 | 哈尔滨工业大学 | 一种硅酸银/(040)钒酸铋直接z型光催化剂及其制备方法和应用 |
Non-Patent Citations (3)
Title |
---|
于谦等: "水热法制备BiVO_4及其光催化性能研究", 《应用化工》 * |
位海棠等: "可见光降解有机污染物催化剂研究进展", 《功能材料》 * |
杨家添等: "水热法制备BiVO4及其可见光催化性能研究", 《玉林师范学院学报(自然科学)》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112547063A (zh) * | 2021-01-08 | 2021-03-26 | 上海大学 | 一种Bi2MoO6Ag2CrO4异质结和制备方法及其作为光催化材料的应用 |
CN113477262A (zh) * | 2021-08-09 | 2021-10-08 | 大连工业大学 | 一种铬酸银/铁酸锌纤维状复合光催化剂的制备方法及应用 |
CN113477262B (zh) * | 2021-08-09 | 2023-09-26 | 大连工业大学 | 一种铬酸银/铁酸锌纤维状复合光催化剂的制备方法及应用 |
CN113856671A (zh) * | 2021-08-26 | 2021-12-31 | 浙江工业大学 | 一种含有s空位的z型异质结光催化剂的制备方法 |
CN113856671B (zh) * | 2021-08-26 | 2023-07-21 | 浙江工业大学 | 一种含有s空位的z型异质结光催化剂的制备方法 |
CN113713823A (zh) * | 2021-09-14 | 2021-11-30 | 蚌埠学院 | 一种CoTiO3/BiVO4复合光催化剂的制备方法及应用 |
Also Published As
Publication number | Publication date |
---|---|
CN111514892B (zh) | 2022-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111514892B (zh) | 一种钒酸铋/铬酸银异质结光催化剂及其制备方法和应用 | |
Xiao | Self-assembly preparation of gold nanoparticles-TiO 2 nanotube arrays binary hybrid nanocomposites for photocatalytic applications | |
Yu et al. | Constructing SrTiO3-T/CdZnS heterostructure with tunable oxygen vacancies for solar-light-driven photocatalytic hydrogen evolution | |
CN105195144B (zh) | 一种合成Au/ZnO棒状异质结光催化剂的方法 | |
Cao et al. | Plasmon-enhanced hydrogen evolution on Au-InVO 4 hybrid microspheres | |
CN109046389B (zh) | 金纳米棒-铂纳米粒子-CdS复合光催化剂及其制备和应用 | |
CN106390986B (zh) | 一种钒酸铋/钛酸锶复合光催化剂的制备方法 | |
CN110479289B (zh) | 一种具有光催化性能的复合型纳米氧化亚铜/氧化锌材料及其制备方法和应用 | |
CN108611653B (zh) | 一种负载磁性纳米粒子的钒酸铋复合材料及其制备和应用 | |
CN113181914B (zh) | 一种过渡金属原位掺杂TiO2催化剂、制备方法及应用 | |
CN112777634B (zh) | 高(010)晶面暴露比钒酸铋的制备方法 | |
CN109078642B (zh) | 一种花型纳米金复合金属氧化物催化剂及其制备方法和应用 | |
Mao et al. | Pt–Ni x alloy nanoparticles: a new strategy for cocatalyst design on a CdS surface for photo-catalytic hydrogen generation | |
CN112675843A (zh) | 一种银量子点复合光催化剂及其制备方法 | |
CN112691656A (zh) | 一种复合光催化剂氧化石墨烯/BiVO4的制备方法 | |
CN115121260A (zh) | 纳米金-氧化亚铜异质结及其制备方法与应用 | |
CN109772394B (zh) | 磷掺杂碳/氧化亚铜复合催化剂及其制备方法和应用 | |
CN111790431A (zh) | 一种以Al2O3修饰的g-C3N4光催化材料的制备方法 | |
Hu et al. | Highly dispersed Cu 2 O quantum dots (about 2 nm) constructed by a simple functional group anchoring strategy boost the photocatalytic water splitting ability by 72 times | |
Jia et al. | Selective growth of TiO 2 beads on Ag nanowires and their photocatalytic performance | |
CN107126953B (zh) | 一种铋/非化学计量比奥里维里斯化合物纳米复合材料及其制备方法和应用 | |
CN113070063B (zh) | 负载金属的三氧化钨基纳米异质结材料的原位合成方法 | |
CN115337942A (zh) | Ag-TiO2/BiOI复合光催化材料的制备方法和应用 | |
CN111871431B (zh) | 一种二硫化锡/金复合催化剂及其制备方法和应用 | |
CN114931941A (zh) | 半导体光催化材料及制备方法与在制备亚胺中的应用 |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |