CN113731387A - 一种处理水中有机污染物的廉价金属/半导体复合光催化剂及制备方法 - Google Patents
一种处理水中有机污染物的廉价金属/半导体复合光催化剂及制备方法 Download PDFInfo
- Publication number
- CN113731387A CN113731387A CN202010459964.8A CN202010459964A CN113731387A CN 113731387 A CN113731387 A CN 113731387A CN 202010459964 A CN202010459964 A CN 202010459964A CN 113731387 A CN113731387 A CN 113731387A
- Authority
- CN
- China
- Prior art keywords
- metal
- semiconductor
- nano
- water
- composite photocatalyst
- 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
- 239000004065 semiconductor Substances 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 title abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002114 nanocomposite Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 22
- 239000002105 nanoparticle Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 108010024636 Glutathione Proteins 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- 229960003180 glutathione Drugs 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 239000007771 core particle Substances 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 32
- 230000000694 effects Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000013110 organic ligand Substances 0.000 abstract 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
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004753 textile Substances 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/33—Indium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/42—Tin
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种新型金属/半导体复合光催化剂及其制备方法，具体涉及一系列能够高效去水中有机污染物的以金属纳米粒子为核心，表面附着宽禁带半导体材料的复合光催化剂，该材料能够有效处理工业排放的有机染料污染物。本发明通过有机物配体使具有紫外光催化的半导体与在紫外区具有表面等离子共振效应的廉价金属纳米粒子相复合，制备出在紫外光的作用下具有较高光催化效果的金属/半导体复合光催化材料。该方法条件温和、工艺简单、环境友好、无需特殊设备。所制备的催化剂具有成本较低、重复性好、并且有着较好的光催化效果的特点，具有良好的应用前景。
Description
技术领域
本发明属于环境处理技术领域，具体涉及一系列能够处理水中有机物的廉价金属/半导体复合材料及其制备方法。
背景技术
随着社会发展，人们生活中越来越依赖各种工业化产品，如塑料、农药、染料、纺织印染品等。然而工业产品的生产过程中会产生大量有机物废水，这些有机物有着较高的毒性，并且不易降解，对水体污染较大。有机物进入水体后，能够被好氧微生物分解，使溶解氧大幅下降，甚至造成缺氧状态、危害水中生物，使大批鱼类死亡。于是，水中有机物的处理十分有意义。目前，光催化技术能够高效、无污染的降解水中有机物。光催化技术的核心材料为半导体材料，其特殊的能带结构使得半导体在特定波长光的照射下产生电子空穴。电子空穴对能够参加降解反应，生成二氧化碳和水，实现无污染的处理水中污染物。
半导体的光催化效率受到光响应范围、量子产率等因素影响，而金属纳米粒子与半导体相复合能够提高半导体的光催化效果。但是人们普遍利用价格昂贵的贵金属如金、银纳米粒子的表面等离子共振效应来增强半导体的光催化活性。但一方面，贵金属价格较高，提高了催化剂的成本。另一方面，金、银纳米粒子的表面等离子共振波长范围普遍在可见光范围内，对于、紫外光才能够响应的宽禁带半导体材料的光催化增强效果具有局限性。
发明内容
本发明提供一种价格低廉、具有较好光催化性能、环境友好的廉价金属/半导体复合材料，该材料制备工艺简单、造价低廉、并且能够有效降解水中有机物。在此基础上，本发明还提供了此复合光催化材料的制备方法。
本发明提出的廉价金属/半导体复合材料其结构特征在于：金属粒子为核心，半导体材料负载在金属粒子表面。
本发明提出的廉价金属/半导体复合光催化材料中，金属与半导体的物质的量比为1:1～1:3。
本发明提出的廉价金属/半导体复合催化材料中，所述的金属应为铝、铟、镁中的一种，粒径为30 nm～100 nm。所述的半导体材料为TiO2、ZnO、SnO2、MnTiO3、In2O3、BaTiO3的一种，尺寸为5～20 nm。
本发明提出的廉价金属/半导体复合催化材料由如下步骤制备。
1）将1～3 mg金属纳米粒子加入15 ml乙醇和水体积比2:1～3:1的混合溶液中，使用细胞粉碎仪超声处理20 min～40 min。
2）上述金属纳米粒子溶液中，加入2.7～22.8 mg配体，在30℃～40℃的温度下，在转速为500 r/min～1500 r/min条件下搅拌15 min～20min。得到表面修饰的金属纳米粒子溶液。
3）将2.9～20.5 mg半导体纳米粒子加入15 ml去离子水中，在转速为500 r/min～1500 r/min条件下搅拌5 min～10min，得到半导体悬浊液。
4）将表面修饰的金属纳米粒子溶液与半导体悬浊液混合，在30℃～40℃的温度下静置1～2 h。得到金属/半导体纳米复合材料的悬浊液。
5）将得到的金属/半导体纳米复合材料的悬浊液在5000～6000 r/min的转速下离心5 min～10 min，除去上清液烘干可得到金属/半导体复合催化材料。
本发明所提供的金属/半导体复合催化剂制备方法中，所述的配体为谷胱甘肽，半胱氨酸，硫代苹果酸中的一种或两种以上的混合物。
与现有技术相比，本发明的优点在于：其中金属与半导体二者通过表面配体相互作用相结合。所以配体的需要具有氨基及羧基特定官能团。金属表面原子与配体的羧基反应形成稳定的化学键，半导体表面羟基官能团也可以和配体的氨基与剩余的羧基反应形成稳定化学键。在实际使用过程中金属和半导体能够结合稳定，保证金属与半导体之间紧密连接，以便发生电子及能量的转移，以提高传统半导体的光催化效率。
本发明金属/半导体纳米复合材料的光催化效率提升机理可解释为：铝、铟、镁等纳米粒子在紫外区间内的介电常数的实部为负、虚部较小，所以此类金属纳米粒子在紫外光范围内有着较强的吸收，并且能够发生表面等离子共振效应，并在其周围产生近场增强效应，半导体纳米粒子受到增强的电磁场作用后，会提高电子空穴产生率。除此之外，金属与半导体相互接触会发生电子转移，从而使半导体表面的能带发生弯曲，产生肖特基势垒。使半导体表面电子耗尽，空穴累积。而电子由于弯曲的能带累积至半导体内部。从而实现电子和空穴的分离，降低了电子空穴复合率。金属/半导体复合光催化体系在提高电子空穴产生率的前提下，同时降低其复合率，促进了光催化反应的进行。
本发明还提供金属/半导体纳米复合光催化剂的制备方法。该方法条件温和、工艺简单、环境友好、无需特殊设备。所制备的催化剂具有成本较低、重复性好、并且有着较好的光催化效果的特点，具有良好的应用前景。
附图说明
图1是本发明实施例1所获得的Al/TiO2纳米复合光催化材料的透射电镜图片。
图2是本发明实施例1所获得的Al/TiO2纳米复合光催化材料的XRD图片。
图3是本发明实施例1所获得的Al/TiO2纳米复合光催化材料对亚甲基蓝的讲解效果图。
具体实施方式
以下实施例中所采用的材料和仪器均为市售，原材料为分析纯。
实施例1：
一种Al/TiO2纳米复合光催化材料，其中包括Al纳米粒子（其尺寸为50-100 nm），TiO2纳米粒子（其尺寸为5 nm-15 nm）。TiO2纳米粒子负载在Al纳米粒子上。
上述施例的Al/TiO2纳米复合光催化材料的制备方法包括以下步骤。
1）在室温条件下配置金属纳米粒子溶液：将1 mg Al纳米粒子加入15 ml乙醇和水体积比2:1的混合溶液中，使用细胞粉碎仪超声处理20min。
2）上述金属纳米粒子溶液中，加入11.4 mg谷胱甘肽配体，在30℃的温度下，在转速为500 r/min条件下搅拌15 min。得到表面修饰的金属纳米粒子溶液。
3）将2.9 mg TiO2纳米粒子加入15 ml去离子水中，在转速为500 r/min条件下搅拌10 min，得到半导体悬浊液。
4）将表面修饰的金属纳米粒子溶液与半导体悬浊液混合，在30 ℃的温度下静置2h。得到Al/TiO2纳米复合材料溶液。
5）将得到的金属/半导体纳米复合材料的悬浊液在6000 r/min的转速下离心5min，除去上清液烘干可得到金属/半导体复合催化材料。
图1为本实施例1所获得的Al/TiO2纳米复合光催化材料的TEM图，可以看出，本发明制备的Al/TiO2纳米复合材料的颗粒大小约为80 nm，表面粗糙。
图2为本实施例1所获得的Al/TiO2纳米复合光催化材料的XRD图，可以看出，Al/TiO2纳米复合材料拥有Al和TiO2的特征峰。
图3为本实施例1所获得的Al/TiO2纳米复合光催化材料在500 w的氙灯的照射下对亚甲基蓝的降解图，可以看出，Al/TiO2纳米复合光催化材料能够在70 min内能够将100ml的1 mg/L的亚甲基蓝溶液降解至原来浓度的1%，比TiO2对亚甲基蓝的降解率有较好的提高。证明了Al/TiO2纳米复合材料的高效光催化性能。
实施例2：
一种In/ZnO纳米复合光催化材料，其中包括In纳米粒子（其尺寸为30-70 nm），ZnO纳米粒子（其尺寸为3 nm-10 nm）。ZnO纳米粒子负载在In纳米粒子上。
上述施例的In/ZnO纳米复合光催化材料的制备方法包括以下步骤。
1）在室温条件下配置金属纳米粒子溶液：将3 mg In纳米粒子加入15 ml乙醇和水体积比3:1的混合溶液中，使用细胞粉碎仪超声处理40min。
2）上述金属纳米粒子溶液中，加入3.9 mg硫代苹果酸配体，在40℃的温度下，在转速为1000 r/min条件下搅拌20 min。得到表面修饰的金属纳米粒子溶液。
3）将6.3 mg ZnO纳米粒子加入15 ml去离子水中，在转速为1000 r/min条件下搅拌5 min，得到半导体悬浊液。
4）将表面修饰的金属纳米粒子溶液与半导体悬浊液混合，在40 ℃的温度下静置1h。得到In/ZnO纳米复合材料溶液。
5）将得到的金属/半导体纳米复合材料的悬浊液在5000 r/min的转速下离心10min，除去上清液烘干可得到金属/半导体复合催化材料。
表格1为实施例2所获得的In/ZnO纳米复合光催化材料在500 w的氙灯的照射下对
亚甲基蓝的降解效果表格。可以看出In/ZnO能够在80 min内能够将100 ml的1 mg/L的亚甲
基蓝溶液降解至原来浓度的1%。
| 降解时间（min） | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 |
| 浓度比 | 100% | 85% | 77% | 63% | 49% | 42% | 29% | 12% | 1% |
表1
实施例3：
一种Al/SnO2纳米复合光催化材料，其中包括Al纳米粒子（其尺寸为50-100 nm），SnO2纳米粒子（其尺寸为5 nm-10 nm）。SnO2纳米粒子负载在Al纳米粒子上。
上述施例的Al/SnO2纳米复合光催化材料的制备方法包括以下步骤。
1）将3 mg金属纳米粒子加入15 ml乙醇和水体积比3:1的混合溶液中，使用细胞粉碎仪超声处理40 min。
2）上述金属纳米粒子溶液中，加入16.7 mg半胱氨酸配体，在30℃的温度下，在转速为1500 r/min条件下搅拌20min。得到表面修饰的金属纳米粒子溶液。
3）将13.5 mg半导体纳米粒子加入15 ml去离子水中，在转速为1500 r/min条件下搅拌5 min，得到半导体悬浊液。
4）将表面修饰的金属纳米粒子溶液与半导体悬浊液混合，在40℃的温度下静置2h。得到金属/半导体纳米复合材料的悬浊液。
5）将得到的金属/半导体纳米复合材料的悬浊液在5000 r/min的转速下离心10min，除去上清液烘干可得到金属/半导体复合催化材料。
表格2为实施例2所获得的Al/SnO2纳米复合光催化材料在500 w的氙灯的照射下
对亚甲基蓝的降解效果表格。可以看出In/ZnO能够在50 min内能够将100 ml的1 mg/L的亚
甲基蓝溶液降解至原来浓度的1%。
| 降解时间（min） | 0 | 10 | 20 | 30 | 40 | 50 |
| 浓度比 | 100% | 75% | 56% | 37% | 18% | 1% |
表2。
Claims (5)
1.一种处理水中有机物的金属/半导体复合光催化剂，其特征在于，核心粒子为金属粒子，外层粒子为半导体纳米材料通过配体与内层的金属相连接。
2.如权利要求1所述的金属/半导体复合光催化剂，其特征在于：所述的金属应为铝、铟、镁中的一种，尺寸为30 nm～100 nm。
3.如权利要求1所述的金属/半导体复合光催化剂，其特征在于：所述的半导体材料为TiO2、ZnO、SnO2、MnTiO3、In2O3、BaTiO3的一种，尺寸为5～20 nm。
4.根据权利要求1-3任意一种金属/半导体复合光催化剂的制备方法，其特征在于：将1～3 mg金属纳米粒子加入15 ml乙醇和水体积比2:1～3:1的混合溶液中，使用细胞粉碎仪超声处理20 min～40 min；在上述金属纳米粒子溶液中，加入11.4～22.8 mg配体，在30℃～40℃的温度下，在转速为500 r/min～1500 r/min条件下搅拌15 min～20min，得到表面修饰的金属纳米粒子溶液；再将2.9～20.5 mg半导体纳米粒子加入15 ml去离子水中，在转速为500 r/min～1500 r/min条件下搅拌5 min～10min，得到半导体悬浊液；将表面修饰的金属纳米粒子溶液与半导体悬浊液混合，在30℃～40℃的温度下静置1～2h，得到金属/半导体纳米复合材料的悬浊液；将得到的金属/半导体纳米复合材料的悬浊液在6000 r/min～7000 r/min的转速下离心5 min～10 min，除去上清液烘干可得到金属/半导体复合催化材料。
5.根据权利要求4所述的金属/半导体复合光催化剂的制备方法，其特征在于，权利要求4步骤2中所提及的配体为谷胱甘肽，半胱氨酸，硫代苹果酸中的一种或两种以上的混合物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010459964.8A CN113731387A (zh) | 2020-05-28 | 2020-05-28 | 一种处理水中有机污染物的廉价金属/半导体复合光催化剂及制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010459964.8A CN113731387A (zh) | 2020-05-28 | 2020-05-28 | 一种处理水中有机污染物的廉价金属/半导体复合光催化剂及制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113731387A true CN113731387A (zh) | 2021-12-03 |
Family
ID=78723657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010459964.8A Pending CN113731387A (zh) | 2020-05-28 | 2020-05-28 | 一种处理水中有机污染物的廉价金属/半导体复合光催化剂及制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113731387A (zh) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003064278A (ja) * | 2001-08-23 | 2003-03-05 | Mitsubishi Chemicals Corp | コアシェル型半導体ナノ粒子 |
| CN1962060A (zh) * | 2005-11-08 | 2007-05-16 | 财团法人工业技术研究院 | 金属纳米光催化剂复合材料及其制法 |
| KR20090035812A (ko) * | 2007-10-08 | 2009-04-13 | 전북대학교산학협력단 | 자외선 및 가시광선 동시응답 이산화티타늄 캡슐형금속나노입자 광촉매 및 그 제조방법 |
| US20120145532A1 (en) * | 2009-07-24 | 2012-06-14 | Stc.Unm | Efficient hydrogen production by photocatalytic water splitting using surface plasmons in hybrid nanoparticles |
| CN102500758A (zh) * | 2011-09-29 | 2012-06-20 | 厦门大学 | 一种金与铜铟硒的核壳纳米晶及其制备方法 |
| CN102816402A (zh) * | 2011-06-09 | 2012-12-12 | 北京化工大学 | 一种高透明紫外阻隔仿陶瓷柔性纳米复合膜材料及其制备方法 |
| JP2013188697A (ja) * | 2012-03-14 | 2013-09-26 | Ishii Kei | 複合型プラズモン金属ナノ粒子及びその用途 |
| CN104492432A (zh) * | 2014-12-13 | 2015-04-08 | 济南大学 | 中空双金属纳米粒子/二氧化钛核壳结构及其制备方法和应用 |
| CN104645980A (zh) * | 2013-11-21 | 2015-05-27 | 中国科学院金属研究所 | 一种贵金属-氧化锌复合材料及其制备方法和应用 |
| CN104916782A (zh) * | 2015-05-25 | 2015-09-16 | 中国科学院半导体研究所 | 采用表面等离激元效应的倒置太阳电池结构及制备方法 |
| CN108160990A (zh) * | 2018-01-05 | 2018-06-15 | 广东工业大学 | 一种核壳结构的纳米颗粒互连材料及其制备方法 |
| US20180299458A1 (en) * | 2015-05-21 | 2018-10-18 | Lamdagen Corporation | Plasmonic nanoparticles and lspr-based assays |
| CN108786792A (zh) * | 2018-06-25 | 2018-11-13 | 福州大学 | 一种金属/半导体复合光催化剂及其制备与应用 |
| CN110385427A (zh) * | 2019-07-31 | 2019-10-29 | 东南大学 | 一种水溶性纳米粒子及其制备方法和应用 |
-
2020
- 2020-05-28 CN CN202010459964.8A patent/CN113731387A/zh active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003064278A (ja) * | 2001-08-23 | 2003-03-05 | Mitsubishi Chemicals Corp | コアシェル型半導体ナノ粒子 |
| CN1962060A (zh) * | 2005-11-08 | 2007-05-16 | 财团法人工业技术研究院 | 金属纳米光催化剂复合材料及其制法 |
| KR20090035812A (ko) * | 2007-10-08 | 2009-04-13 | 전북대학교산학협력단 | 자외선 및 가시광선 동시응답 이산화티타늄 캡슐형금속나노입자 광촉매 및 그 제조방법 |
| US20120145532A1 (en) * | 2009-07-24 | 2012-06-14 | Stc.Unm | Efficient hydrogen production by photocatalytic water splitting using surface plasmons in hybrid nanoparticles |
| CN102816402A (zh) * | 2011-06-09 | 2012-12-12 | 北京化工大学 | 一种高透明紫外阻隔仿陶瓷柔性纳米复合膜材料及其制备方法 |
| CN102500758A (zh) * | 2011-09-29 | 2012-06-20 | 厦门大学 | 一种金与铜铟硒的核壳纳米晶及其制备方法 |
| JP2013188697A (ja) * | 2012-03-14 | 2013-09-26 | Ishii Kei | 複合型プラズモン金属ナノ粒子及びその用途 |
| CN104645980A (zh) * | 2013-11-21 | 2015-05-27 | 中国科学院金属研究所 | 一种贵金属-氧化锌复合材料及其制备方法和应用 |
| CN104492432A (zh) * | 2014-12-13 | 2015-04-08 | 济南大学 | 中空双金属纳米粒子/二氧化钛核壳结构及其制备方法和应用 |
| US20180299458A1 (en) * | 2015-05-21 | 2018-10-18 | Lamdagen Corporation | Plasmonic nanoparticles and lspr-based assays |
| CN104916782A (zh) * | 2015-05-25 | 2015-09-16 | 中国科学院半导体研究所 | 采用表面等离激元效应的倒置太阳电池结构及制备方法 |
| CN108160990A (zh) * | 2018-01-05 | 2018-06-15 | 广东工业大学 | 一种核壳结构的纳米颗粒互连材料及其制备方法 |
| CN108786792A (zh) * | 2018-06-25 | 2018-11-13 | 福州大学 | 一种金属/半导体复合光催化剂及其制备与应用 |
| CN110385427A (zh) * | 2019-07-31 | 2019-10-29 | 东南大学 | 一种水溶性纳米粒子及其制备方法和应用 |
Non-Patent Citations (1)
| Title |
|---|
| MITSUHIRO HONDA ET AL.: "Plasmon-enhanced UV photocatalysis", APPLIED PHYSICS LETTERS, vol. 104, pages 061108 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | A novel step-scheme BiVO4/Ag3VO4 photocatalyst for enhanced photocatalytic degradation activity under visible light irradiation | |
| Narzary et al. | Visible light active, magnetically retrievable Fe3O4@ SiO2@ g-C3N4/TiO2 nanocomposite as efficient photocatalyst for removal of dye pollutants | |
| Scott et al. | Photocatalytic degradation of phenol in water under simulated sunlight by an ultrathin MgO coated Ag/TiO2 nanocomposite | |
| Huang et al. | Preparation and characterization of Cu2O/TiO2 nano–nano heterostructure photocatalysts | |
| CN107442178B (zh) | 一种可见光催化剂Fe3O4@PDA@Ag复合微球的制备方法 | |
| CN109692698B (zh) | 一种催化还原NOx的Bi/Ti3C2纳米片状光催化剂及其制备方法 | |
| Chen et al. | The BiOBr/Bi/Bi2WO6 photocatalyst with SPR effect and Z-scheme heterojunction synergistically degraded RhB under visible light | |
| Alburaih et al. | Facile synthesis of W1-yFeyO3@ NiO@ RGO ternary nanohybrid with enhanced sunlight mediated photocatalytic and bactericidal activities for water purification | |
| Yang et al. | In-situ generation of oxygen vacancies and Bi0 clusters on MoSe2/Bi@ BiOBr-OV via Fermi inter-level electron transfer for efficient elimination of chlorotetracycline and Cr (VI) | |
| Lu et al. | A novel preparation of GO/NiFe2O4/TiO2 nanorod arrays with enhanced photocatalytic activity for removing unsymmetrical dimethylhydrazine from water | |
| Nuengmatcha et al. | Efficient degradation of dye pollutants in wastewater via photocatalysis using a magnetic zinc oxide/graphene/iron oxide-based catalyst | |
| Jabbar et al. | Reasonable decoration of CuO/Cd0. 5Zn0. 5S nanoparticles onto flower-like Bi5O7I as boosted step-scheme photocatalyst for reinforced photodecomposition of bisphenol A and Cr (VI) reduction in wastewater | |
| Tu et al. | Synthesis of Fe2O3/TiO2/graphene aerogel composite as an efficient Fenton‐photocatalyst for removal of methylene blue from aqueous solution | |
| CN113198515B (zh) | 一种三元光催化剂及其制备方法与应用 | |
| Sun et al. | Microwave in-situ liquid-phase deposition of Cu2O/Tg-C3N4 heterojunction for enhancing visible light photocatalytic degradation of tetracycline | |
| CN108079990B (zh) | 一种二氧化钛包覆铜纳米复合材料及其制备方法和应用 | |
| Wang et al. | Preparation of a high-performance N-defect ZnO@ g-C3N4 nanocomposite and its photocatalytic degradation of tetracycline | |
| CN110316806B (zh) | 一种用于水中硝酸盐氮去除的纳米复合材料nZVFPG及其制备方法和应用 | |
| CN104368338A (zh) | 一种具有氨基修饰的Pd/TiO2光催化剂的制备方法 | |
| Mukherjee et al. | Graphene quantum dots decorated MIL-100 (Fe) composites for dye degradation | |
| CN104826639B (zh) | 磷酸银/还原石墨烯/二氧化钛纳米复合材料及制备方法 | |
| CN113731387A (zh) | 一种处理水中有机污染物的廉价金属/半导体复合光催化剂及制备方法 | |
| CN109331803B (zh) | 二氧化钛-石墨烯复合材料及其在光触媒纳米溶胶中的应用 | |
| CN108620101A (zh) | Ag/PbBiO2Cl纳米片复合光催化剂及制备方法 | |
| CN109365005B (zh) | 高催化降解性能光触媒水溶胶及其生产工艺 |
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: 20211203 |
|
| WD01 | Invention patent application deemed withdrawn after publication |