CN111233028A - 一种超亲水-超疏水可控的zis纳米分级材料的制备方法及其应用 - Google Patents
一种超亲水-超疏水可控的zis纳米分级材料的制备方法及其应用 Download PDFInfo
- Publication number
- CN111233028A CN111233028A CN202010119012.1A CN202010119012A CN111233028A CN 111233028 A CN111233028 A CN 111233028A CN 202010119012 A CN202010119012 A CN 202010119012A CN 111233028 A CN111233028 A CN 111233028A
- Authority
- CN
- China
- Prior art keywords
- zis
- nano
- super
- csnh
- hydrophilic
- 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
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 14
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 7
- 239000011686 zinc sulphate Substances 0.000 claims abstract description 7
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- KYCHGXYBBUEKJK-UHFFFAOYSA-K indium(3+);trichloride;hydrate Chemical compound O.Cl[In](Cl)Cl KYCHGXYBBUEKJK-UHFFFAOYSA-K 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 claims description 4
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 8
- 231100001240 inorganic pollutant Toxicity 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 description 29
- 239000004098 Tetracycline Substances 0.000 description 17
- 229960002180 tetracycline Drugs 0.000 description 17
- 229930101283 tetracycline Natural products 0.000 description 17
- 235000019364 tetracycline Nutrition 0.000 description 17
- 239000011651 chromium Substances 0.000 description 14
- 238000007146 photocatalysis Methods 0.000 description 14
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 14
- 239000002086 nanomaterial Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 8
- 229940012189 methyl orange Drugs 0.000 description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 150000003522 tetracyclines Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- 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
- B01J27/04—Sulfides
-
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种超亲水‑超疏水可控的ZIS纳米分级材料的制备方法及其应用,是以InCl3·4H2O、ZnSO4·7H2O和CH3CSNH2为原料,经一步水热反应,获得Zn3In2S6纳米分级材料;通过调控原料中CH3CSNH2的添加量,来实现所得Zn3In2S6(ZIS)纳米分级材料表面亲水或疏水特性的调控。在可见光照下,本发明所得表面超亲水的ZIS显示了优异的水体中有机/无机污染物去除活性,而所得表面超疏水的ZIS显示了优异的大气中污染物的转化活性。
Description
技术领域
本发明涉及纳米材料表面亲疏水调控和光催化技术领域,具体涉及一种超亲水-超疏水可控的Zn3In2S6纳米分级材料的制备方法及其在环境及光催化领域上的应用。
背景技术
化学品的过度使用(如我国印染企业每天排放的染料废水量达300万~400万吨)和CO2排放的快速增长(如2019年5月,大气中的CO2浓度已经超过415ppm,即CO2质量超过整个大气质量的万分之4.15)致使环境污染及气候变化日益严峻。据统计,每年我国因为生态破坏和环境污染造成的经济损失高达6000亿元。2019年,仅污染防治费用,中央财政安排预算就高达600亿元。环境污染已经成为严重威胁我国经济和生态建设的重大问题。解决环境污染问题是我国实现经济和生态建设、改善人民生活质量的迫切需要。
水体污染和大气污染备受关注,其中水体污染中最为常见的有肉眼可见的染料类化合物以及无色的有机污染物如抗生素、环境类激素等;大气污染中的CO2浓度的快速增长带来的温室效应和生态的严重破坏;又如大气中氮氧化物(如NO2)含量的增长带来的臭氧层的破坏和对人类及其它生物的严重危害等。环境污染物的去除受到了世界多个学科领域的高度、持续和广泛关注。相对于传统的物理吸附法、生物降解法、化学氧化分解法,半导体光催化技术受到了越来越广泛的关注,半导体光催化技术可利用取之不竭的太阳能在温和的条件下激发半导体催化剂产生光生电子、空穴、羟基自由基和超氧自由基反应活性物质,将有机/无机污染物降解/转化为二氧化碳、水或者其它有用的化学品。光催化技术因其绿色、高效、成本低、操作简单、不会产生二次污染等特点而引起世界科研工作者极大的研究兴趣;加之能源和环境问题是全球关注的焦点,而光催化技术可以直接利用清洁可再生的太阳能,因此成为科学技术研究的热点。然而,目前已报道的光催化剂光催化效率较低,相较于实际应用,高效可见光响应型光催化剂的开发依然亟待解决。
半导体光催化反应是在半导体催化剂表面进行的反应,半导体催化剂的表面特性直接决定了某一催化反应能否发生以及催化反应的效率,而反应物被化学吸附在催化剂的表面上是催化反应的首要先决条件。因此,催化剂的表面设计对于催化反应至关重要。比如,水体中有机污染物的光催化去除要求半导体催化剂务必能分散于水中,即具有一定的亲水性;而对于非极性分子或者疏水分子的催化反应要求半导体催化剂表面务必具有疏水特性。因此,调控半导体纳米材料表面的亲疏水特性也许是实现环境污染物光催化高效去除的一个新途径。
二维(2D)金属硫化物Zn3In2S6(ZIS)因其独特的结构、物理、化学特性而在多个研究领域备受关注。作为光催化剂,2D ZIS不仅能被可见光激发、大的比表面和丰富的负载位点、适宜的能带结构,而且具有优异的光电特性,显示了ZIS在光催化领域的潜在应用。然而,ZIS单体的光催化性能并不高。为了提升其光催化活性,目前多是采用纳米材料复合的方法,比如ZIS@ZnO、Au/ZIS和Ptx/ZIS等。
如何对于ZIS表面亲疏水特性进行调控还不曾见报道。
发明内容
针对现有技术的不足,本发明旨在提供一种简便的Zn3In2S6(ZIS)纳米材料表面亲水-疏水调控策略及其在光催化和环境修复领域上的应用,所要解决的问题是ZIS表面超亲水-超疏水的调控和环境污染物光催化去除效率提高的问题。
为解决现有技术的问题,本发明采取的技术方案为:
一种超亲水-超疏水可控的ZIS纳米分级材料的制备方法,其特点在于:以水合氯化铟InCl3·4H2O、水合硫酸锌ZnSO4·7H2O和硫代乙酰胺CH3CSNH2为原料,经一步水热反应,获得Zn3In2S6纳米分级材料;通过调控原料中硫代乙酰胺CH3CSNH2的用量,来调控所得Zn3In2S6纳米分级材料的表面亲水或疏水特性。具体包括如下步骤:
步骤1、称取2mmol水合氯化铟InCl3·4H2O、3mmol水合硫酸锌ZnSO4·7H2O、0.65g十六烷基溴化铵CTAB和7-30mmol的硫代乙酰胺CH3CSNH2于烧杯中,然后再加入70mL去离子水,搅拌均匀,得到混合溶液;
步骤2、将所述混合溶液倒入内衬有聚四氟乙烯的100mL反应釜中,密封,160℃水热反应12h;反应结束后,冷却至室温,所得产物经洗涤、干燥,即获得Zn3In2S6纳米分级材料。
进一步地,当步骤1中CH3CSNH2的用量为7-12mmol时,所得产物为表面亲水Zn3In2S6纳米分级材料;当步骤1中CH3CSNH2的用量为15-30mmol时,所得产物为表面疏水Zn3In2S6纳米分级材料。通过调控CH3CSNH2的用量,实现了Zn3In2S6纳米分级材料由超亲水向超疏水的转变。
进一步地,步骤2中,所述洗涤是用去离子水和无水乙醇交替洗涤数次,所述干燥是放真空干燥箱60℃干燥12h。
本发明设计制备了表面超亲水-超疏水可调控的ZIS纳米分级结构材料——超亲水性的2D/3D分级结构ZIS(记为ZIS-Q)和超疏水性的0D/2D/3D结构ZIS(记为ZIS-S)。ZIS表面的亲-疏水特性使其在可见光光催化去除水体有机/无机污染物和转化大气污染物中分别显示了显著的活性差异性和污染物的去除活性。ZIS-Q显示了优异的水体中有机/无机污染物(如甲基橙、四环素和六价铬中的至少一种)去除活性,而ZIS-S显示了优异的大气中污染物(如CO2和NO2中的至少一种)的转化活性。在可见光照下60秒,ZIS-Q可以100%去除水体中同时存在的四环素(TC)和六价铬(Cr(VI))。ZIS-S在可见光照下,则几乎可将大气中NO2完全转化为硝酸根。因此,ZIS-Q和ZIS-S显示了在环境净化不同领域的潜在应用。另一个方面,纳米材料表面的亲疏水特性在自清洁、防腐蚀、防覆冰、防雾、防生物污垢、油水分离、热传递、细胞捕获、绿色打印传感及能源转化等新兴领域亦有重大潜在应用。
与现有技术相比,本发明的有益效果体现在:
1、本发明的制备方法步骤简便,一步水热反应即可实现ZIS纳米材料表面的超亲-疏水调控,为其它纳米材料的表面调控提供了一种简便的可供借鉴的新策略;
2、本发明对ZIS表面亲-疏水进行了调控,在可见光照下,ZIS-Q显示了优异的水体中有机/无机污染物去除活性,而ZIS-S显示了优异的大气中污染物的转化活性。
附图说明
图1为实施例1合成ZIS-Q和实施例2合成ZIS-S的接触角实验;
图2为实施例1合成ZIS-Q和实施例2合成ZIS-S的XRD图;
图3为实施例1合成ZIS-Q和实施例2合成ZIS-S的EDS谱;
图4为实施例1合成ZIS-Q(a)和实施例2合成ZIS-S(b)的SEM图;
图5为实施例1合成ZIS-Q(a)和实施例2合成ZIS-S(b)的TEM图;
图6为实施例1合成ZIS-Q(a)和实施例2合成ZIS-S(b)的放大TEM图;
图7为实施例1合成ZIS-Q和实施例2合成ZIS-S可见光光催化降解MO活性图;
图8为实施例1合成ZIS-Q和实施例2合成ZIS-S可见光光催化降解TC活性图;
图9为实施例1合成ZIS-Q和实施例2合成ZIS-S可见光光催化降解Cr(VI)活性图;
图10为实施例1合成ZIS-Q和实施例2合成ZIS-S可见光光催化降解TC-Cr(VI)混合液的活性图:(a)和(b)分别是混合液中TC和Cr(VI)的降解曲线;
图11为实施例1合成ZIS-Q和实施例2合成ZIS-S可见光光催化还原CO2活性图;
图12为实施例1合成ZIS-Q和实施例2合成ZIS-S可见光光催化去除NO2的原位红外谱;
图13为实施例1合成ZIS-Q和实施例2合成ZIS-S的亲水和疏水原理示意图及其可见光光催化去除MO、TC、Cr(VI)、CO2和NO2的示意图。
具体实施方式
下面结合具体实施例对本发明进一步说明,具体实施例的描述本质上仅仅是范例,以下实施例基于本发明技术方案进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
本实施例按如下步骤制备超亲水ZIS纳米分级材料(记为ZIS-Q):
步骤1、称取2mmol InCl3·4H2O、3mmol ZnSO4·7H2O、0.65g CTAB和7mmol的CH3CSNH2于烧杯中,然后再加入70mL去离子水,搅拌均匀,得到混合溶液;
步骤2、将混合溶液倒入内衬有聚四氟乙烯的100mL反应釜中,密封,160℃水热反应12h;反应结束后,冷却至室温,所得产物用去离子水和无水乙醇交替洗涤数次,最后放真空干燥箱60℃干燥12h,收集样品,即获得ZIS-Q。
实施例2
本实施例按如下步骤制备超疏水ZIS纳米材料(记为ZIS-S):
步骤1、称取2mmol InCl3·4H2O、3mmol ZnSO4·7H2O、0.65g CTAB和30mmol的CH3CSNH2于烧杯中,然后再加入70mL去离子水,搅拌均匀,得到混合溶液;
步骤2、将混合溶液倒入内衬有聚四氟乙烯的100mL反应釜中,密封,160℃水热反应12h;反应结束后,冷却至室温,所得产物用去离子水和无水乙醇交替洗涤数次,最后放真空干燥箱60℃干燥12h,收集样品,即获得ZIS-S。
实施例3
本实施例按如下步骤测试ZIS可见光光催化降解甲基橙(MO)的性能:
步骤1、将50mL、20ppm的MO水溶液加入到250mL的玻璃烧杯中;
步骤2、称取50mg的ZIS加入到上述溶液中;
步骤3、在无光照条件下,超声分散,并在暗态条件下,搅拌30分钟完成吸附-脱附的动态平衡;
步骤4、开灯,光照(光为波长大于400nm的可见光),并在给定的间隔时间后取混合悬浮液3mL,
步骤5、将3mL的悬浮液进行离心,取上清液,用紫外-可见分光光度计测其吸光度。
步骤6、根据下面公式计算MO光催化降解率:
降解率=(1-Ct/C0)×100%
C0和Ct分别是光催化反应前溶液中污染物的浓度和光催化反应后溶液中污染物的浓度。
实施例4
本实施例按如下步骤测试ZIS可见光光催化降解四环素(TC)的性能:
本例与实施例3相同,不同之处在于步骤1中加入的为20ppm的TC水溶液。
实施例5
本实施例按如下步骤测试ZIS可见光光催化降解重铬酸根中的六价铬(Cr(VI))的性能:
本例与实施例3相同,不同之处在于步骤1中加入的为20ppm的重铬酸钾水溶液,步骤5中采用国标(GBT 7467-1987)二苯碳酸二阱分光光度法测Cr(VI)吸光度。
实施例6
本实施例按如下步骤测试ZIS可见光光催化同时降解TC和Cr(VI)的性能:
本例与实施例3相同,不同之处在于步骤1中加入的为25mL、20ppm的TC水溶液和25mL、20ppm的重铬酸钾水溶液的混合液,以及步骤5的3mL上清液分别用紫外-可见分光光度计测TC吸光度和采用国标(GBT 7467-1987)二苯碳酸二阱分光光度法测Cr(VI)吸光度。
实施例7
本实施例按如下步骤测试ZIS可见光光催化还原CO2的性能:
步骤1、将50mg ZIS、20mg 2,2-联吡啶、4mL乙腈、2mL水和1mL三乙醇胺加入可通气/放气带石英窗的光催化反应池;
步骤2、通入CO2气体,并在搅拌条件下吹扫30min;
步骤3、开灯,光照(光为波长大于400nm的可见光),并在给定的间隔时间通过气相色谱检测CO2还原产物。
实施例8
本实施例按如下步骤测试ZIS可见光光催化氧化NO2的性能:
步骤1、将50mg ZIS置于小坩埚中,并用干燥高纯空气吹扫10分钟去除样品表面的水分和杂质;
步骤2、通入NO2气体(55ppm)和高纯空气到反应室中;
步骤3、待暗态达到吸附-脱附平衡后,开灯,光照(光为波长大于400nm的可见光),并用原位红外光谱仪(Shimadzu Tracer-100 FTIR)和离子色谱检测生成物。
纳米材料ZIS-Q和ZIS-S的表征
图1为亲水性接触角实验结果。如图所示,ZIS-Q和ZIS-S的接触角分别为4°和160°。亲/疏水定义为:接触角小于90°称为亲水,小于5°称为超亲水;接触角大于90°称为疏水,大于150°称为超疏水。因此,本发明制备的ZIS-Q具有表面超亲水特性,而ZIS-S具有表面超疏水特性。通过简单的改变反应原料硫源的添加量即可实现ZIS表面亲疏水性的调控,此简便的方法为纳米材料的表面调控提供了新的途径。
图2为ZIS-Q和ZIS-S的X-射线粉末衍射(XRD)谱。ZIS-Q和ZIS-S的XRD峰类似且都和六方相Zn3In2S6的标准XRD峰(JCPDS No.65-4003)一致。其中,23.5、26.9、28.2、46.9、55.8和75.9°分别对应于六方相Zn3In2S6的(005)、(011)、(102)、(110)、(1010)和(0114)晶面。说明本发明制备的ZIS为纯相的Zn3In2S6。进一步的通过能量色散X-射线光谱(EDS)表征(图3)可见ZIS-Q和ZIS-S均是由Zn、In和S三种元素构成。C元素的EDS峰来自测试用的碳导电胶。因此,由图2和3可知:本发明制备的ZIS-Q和ZIS-S均为纯的Zn3In2S6。
为了揭示ZIS表面亲-疏水特性与其结构关系,本发明进一步对其进行了扫描电镜(SEM)和透射电镜(TEM)表征。从图4、图5和图6可见,ZIS-Q为类似牡丹花的2D/3D分级结构,ZIS-Q是由可弯曲的平滑的二维(2D)纳米片交错形成的三维(3D)球形结构。而ZIS-S形貌类似小粒子填满花瓣空隙的牡丹花的0D/2D/3D结构,即很多零维(0D)小纳米颗粒填满了由2D纳米片交错形成的空隙的表面粗糙的3D球形结构。正是由于ZIS-Q和ZIS-S微纳米多级结构的差别决定了其是否具有超浸润特性。
通过以上结果可知,具有超亲水性的2D/3D分级结构ZIS-Q和具有超疏水性的0D/2D/3D结构ZIS-S被成功制备。催化反应发生在催化剂表面,也正因此,催化剂的表面特性对于催化反应至关重要。催化剂表面的特性决定着反应的催化效率。
纳米材料ZIS-Q和ZIS-S的催化活性测试
为了进一步考察ZIS表面亲-疏水特性对催化反应的潜在应用,实施例3~8分别测试了ZIS-Q和ZIS-S对水体中有机/无机污染物光催化去除和大气中CO2和NO2气体可见光催化转化的催化性能。
如图7所示,在可见光照3.5分钟后,20ppm的MO可以被ZIS-Q完全降解(降解率100%),而ZIS-S的降解率只有64%。类似的结果可见可见光光催化降解TC,如图8所示,ZIS-Q和ZIS-S可见光光催化降解TC的降解率分别为91%和68%。由此可见,ZIS表面的超亲水特性可以实现水体中有机物污染物(不论是染料还是抗生素)的高效降解。水体污染物中除了有机物还有无机污染物,比如常见的Cr(VI)。为此本发明进一步测试了ZIS去除Cr(VI)的可见光催化性能,如图9所示,ZIS-Q显示了优越的Cr(VI)去除性能。在可见光照60秒后,ZIS-Q可以实现Cr(VI)的100%去除。为了更进一步的考察ZIS-Q在环境光催化中的潜在应用,本发明又测试了ZIS可见光光催化降解TC和Cr(VI)的混合液,如图10所示,在可见光照60秒,ZIS-Q同时去除TC和Cr(VI)的效率均为100%,而ZIS-S去除TC和Cr(VI)效率分别为82%和85%。通过以上的实验说明了ZIS-Q的表面亲水性可以实现水体中有机污染物、无机重金属离子以及有机-无机污染物的混合物的高效降解,显示了ZIS-Q在污水净化领域的潜在应用。
本发明的ZIS-S具有超疏水性,在水体中污染物去除方面活性较差,可能是因为ZIS-S的疏水性不能使其很好的溶于带有极性的水中。那么,ZIS-S也许对非极性的CO2和弱极性的NO2的去除会有很好的催化效果。为了证实这个想法,本发明测试了ZIS-S可见光光催化还原CO2和氧化NO2的活性。如图11所示,在可见光照射下,ZIS-S可以将CO2有效的还原为CO和H2(CO和H2是水煤气的主要组分和重要的化工原料),CO(71.76μmol/h)和H2(12.73μmol/h)的产生速率是ZIS-Q的11.6和12.2倍。图12为ZIS-S和ZIS-Q去除NO2的原位红外谱图。1392和1423cm-1分别对应于亚硝酸根(NO2 -)和硝酸根(NO3 -)的红外峰。由图可见,在可见光照下,ZIS-S可将NO2氧化为硝酸根,而亚硝酸根的峰几乎没有出现。亚硝酸根的峰则可以明显的在ZIS-Q上看到,说明ZIS-Q可见光催化不能完全氧化NO2为硝酸根,同时还生成了亚硝酸根。通过离子色谱检测,ZIS-S可见光催化氧化NO2生成1.12ppm的硝酸根,约是ZIS-Q活性的2倍。
从上述结果可知,ZIS-Q的2D/3D分级结构有着超亲水特性(图13),而0D/2D/3D结构的ZIS-S表现为超疏水特性。亲水性ZIS(ZIS-Q)有着优异的水体中有机/无机污染物去除活性,而疏水性ZIS(ZIS-S)有着优异的大气中CO2和NO2的转化活性。显示了ZIS-Q和ZIS-S在环境净化不同领域的潜在应用。此外,本发明ZIS-Q和ZIS-S制备方法简便、易行,适合产业化。
Claims (5)
1.一种超亲水-超疏水可控的ZIS纳米分级材料的制备方法,其特征在于:以水合氯化铟InCl3·4H2O、水合硫酸锌ZnSO4·7H2O和硫代乙酰胺CH3CSNH2为原料,经一步水热反应,获得Zn3In2S6纳米分级材料;
通过调控原料中硫代乙酰胺CH3CSNH2的添加量,来调控所得Zn3In2S6纳米分级材料的表面亲水或疏水特性。
2.根据权利要求1所述的制备方法,其特征在于:包括如下步骤:
步骤1、称取2mmol水合氯化铟InCl3·4H2O、3mmol水合硫酸锌ZnSO4·7H2O、0.65g十六烷基溴化铵CTAB和7-30mmol的硫代乙酰胺CH3CSNH2于烧杯中,然后再加入70mL去离子水,搅拌均匀,得到混合溶液;
步骤2、将所述混合溶液倒入内衬有聚四氟乙烯的100mL反应釜中,密封,160℃水热反应12h;反应结束后,冷却至室温,所得产物经洗涤、干燥,即获得Zn3In2S6纳米分级材料。
3.根据权利要求2所述的制备方法,其特征在于:当步骤1中CH3CSNH2的用量为7-12mmol时,所得产物为表面亲水Zn3In2S6纳米分级材料;当步骤1中CH3CSNH2的用量为15-30mmol时,所得产物为表面疏水Zn3In2S6纳米分级材料。
4.根据权利要求2所述的制备方法,其特征在于:步骤2中,所述洗涤是用去离子水和无水乙醇交替洗涤数次,所述干燥是放真空干燥箱60℃干燥12h。
5.一种权利要求1~4中任意一项所得ZIS纳米分级材料的应用,其特征在于:当为表面亲水Zn3In2S6纳米分级材料时,用于作为光催化剂,去除水体中的污染物;当为表面疏水Zn3In2S6纳米分级材料时,用于作为光催化剂,去除大气中的污染物。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010119012.1A CN111233028A (zh) | 2020-02-26 | 2020-02-26 | 一种超亲水-超疏水可控的zis纳米分级材料的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010119012.1A CN111233028A (zh) | 2020-02-26 | 2020-02-26 | 一种超亲水-超疏水可控的zis纳米分级材料的制备方法及其应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111233028A true CN111233028A (zh) | 2020-06-05 |
Family
ID=70878383
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010119012.1A Pending CN111233028A (zh) | 2020-02-26 | 2020-02-26 | 一种超亲水-超疏水可控的zis纳米分级材料的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111233028A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112657515A (zh) * | 2021-01-04 | 2021-04-16 | 辽宁大学 | 3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3及其制备方法和应用 |
CN115228470A (zh) * | 2022-07-01 | 2022-10-25 | 重庆工商大学 | 一种超疏水超亲油羰基铁负载纳米二氧化钛光催化剂的制备方法 |
-
2020
- 2020-02-26 CN CN202010119012.1A patent/CN111233028A/zh active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112657515A (zh) * | 2021-01-04 | 2021-04-16 | 辽宁大学 | 3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3及其制备方法和应用 |
CN112657515B (zh) * | 2021-01-04 | 2023-12-08 | 辽宁大学 | 3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3及其制备方法和应用 |
CN115228470A (zh) * | 2022-07-01 | 2022-10-25 | 重庆工商大学 | 一种超疏水超亲油羰基铁负载纳米二氧化钛光催化剂的制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhang et al. | Influence of BiOIO3 morphology on the photocatalytic efficiency of Z-scheme BiOIO3/g-C3N4 heterojunctioned composite for Hg0 removal | |
Chen et al. | Fabrication and characterization of ZnTiO3/Zn2Ti3O8/ZnO ternary photocatalyst for synergetic removal of aqueous organic pollutants and Cr (VI) ions | |
Saleh | ZnO nanospheres based simple hydrothermal route for photocatalytic degradation of azo dye | |
Bozetine et al. | Green chemistry approach for the synthesis of ZnO–carbon dots nanocomposites with good photocatalytic properties under visible light | |
Feng et al. | 3D MXene/Ag2S material as Schottky junction catalyst with stable and enhanced photocatalytic activity and photocorrosion resistance | |
Beura et al. | Structural, optical and photocatalytic properties of graphene-ZnO nanocomposites for varied compositions | |
Wang et al. | Hollow spherical WO3/TiO2 heterojunction for enhancing photocatalytic performance in visible-light | |
Wang et al. | Superhydrophobic and photocatalytic synergistic Self-Cleaning ZnS coating | |
Jiang et al. | Construction of amorphous Ta2O5/g-C3N4 nanosheet hybrids with superior visible-light photoactivities for organic dye degradation and mechanism insight | |
Zhu et al. | Efficient degradation of tetracycline by RGO@ black titanium dioxide nanofluid via enhanced catalysis and photothermal conversion | |
Thirumalai et al. | Superior photocatalytic, electrocatalytic, and self-cleaning applications of Fly ash supported ZnO nanorods | |
CN107029770B (zh) | 一种亚稳相铋氧化物的制备方法及其在光催化降解有机污染物中的应用 | |
Zhu et al. | Novel methods of sewage sludge utilization for photocatalytic degradation of tetracycline-containing wastewater | |
CN110639555A (zh) | 一种可见光响应的CdS/CdIn2S4复合纳米结构光催化剂的制备方法及应用 | |
CN111233028A (zh) | 一种超亲水-超疏水可控的zis纳米分级材料的制备方法及其应用 | |
Ennaceri et al. | Deposition of multifunctional TiO2 and ZnO top-protective coatings for CSP application | |
Xie et al. | Functions of boric acid in fabricating TiO2 for photocatalytic degradation of organic contaminants and hydrogen evolution | |
CN111250094A (zh) | 双Z型Co3O4/NiCo2O4/NiO光催化剂及其制备方法和应用 | |
Li et al. | Efficient photocathodic protection of nanoflower MgIn2S4-modified CNNs composites on 316 SS under visible light | |
CN110026207B (zh) | CaTiO3@ZnIn2S4纳米复合材料及其制备方法与应用 | |
CN113426461B (zh) | 银掺杂多晶面铁酸锌光催化纳米材料的制备方法 | |
Lv et al. | 2D/2D MoS2/ZnIn2S4 heterojunction for simultaneous realization of solar water evaporation and photocatalytic dye degradation | |
Guo et al. | Enhanced photocatalytic nitrogen fixation of etched Ag-doped PM-CdS catalyst under visible light irradiation | |
Wang et al. | Enhanced photocatalytic performance of persimmon cake like oxygen vacancies enriched NiO/BiVO4 heterojunctions benefited from S-scheme interfacial charge pairs separation and transfer mechanism | |
Chen et al. | In situ growing Cu2 (OH) 2CO3 on oxidized carbon nitride with enhanced photocatalytic hydrogen evolution and pollutant degradation |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200605 |