CN109647378A - 一种用于去除异味硫化氢的纳米片自组装微米球光催化材料的制备方法 - Google Patents
一种用于去除异味硫化氢的纳米片自组装微米球光催化材料的制备方法 Download PDFInfo
- Publication number
- CN109647378A CN109647378A CN201811539341.0A CN201811539341A CN109647378A CN 109647378 A CN109647378 A CN 109647378A CN 201811539341 A CN201811539341 A CN 201811539341A CN 109647378 A CN109647378 A CN 109647378A
- Authority
- CN
- China
- Prior art keywords
- nanometer sheet
- self assembly
- hydrogen sulfide
- preparation
- micron ball
- 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000001338 self-assembly Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 235000019645 odor Nutrition 0.000 title claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 title claims description 14
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title abstract description 38
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- UVAUHTUDFIJIDS-UHFFFAOYSA-N FC(C(C(C(F)(F)F)(F)F)(F)F)([K])F Chemical compound FC(C(C(C(F)(F)F)(F)F)(F)F)([K])F UVAUHTUDFIJIDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910020350 Na2WO4 Inorganic materials 0.000 claims abstract description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000005119 centrifugation Methods 0.000 claims abstract 2
- 229910001868 water Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000007605 air drying Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 pharmacy Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- ZJQKCVGECJBSKT-UHFFFAOYSA-N butane-1-sulfonic acid;potassium Chemical compound [K].CCCCS(O)(=O)=O ZJQKCVGECJBSKT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000189 neurotoxic Toxicity 0.000 description 1
- 230000002887 neurotoxic effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种WO3·H2O纳米片自组装微米球光催化剂的水热制备方法,其特征在于制备的步骤为:1)WO3·H2O的前驱物的制备:将一定量的Na2WO4·2H2O溶于一定量的去离子水中,在搅拌下加入一定量的全氟丁基磺酸钾和柠檬酸,充分搅拌后加入稀盐酸,充分搅拌。2)在温度为60‑150℃,前驱物水热反应4‑50 h。然后将产物离心、水洗、于60℃下空气中干燥。本发明获得了WO3·H2O纳米片自组装而成的微米球催化剂材料,该光催化剂具备高效稳定的光催化性能用于去除异味硫化氢。
Description
技术领域
本发明属于光催化材料技术领域,具体涉及一种用于去除异味硫化氢的WO3·H2O纳米片自组装微米球光催化材料的制备方法。
背景技术
硫化氢(H2S)是高度腐蚀性和刺激性的有毒害气体, 往往很低浓度的H2S就可对人身健康和自然界造成严重的危害,是许多工业生产中的副产品。 例如,石油精炼、天然气净化、皮革制造、橡胶合成、煤气制取、造纸、石油化工、化肥、制药、污水处理和垃圾处理等等过程中都会产生大量硫化氢恶臭气体,不仅严重影响人们的日常生活,危害人体健康,同时也污染环境。H2S在空气中的最高容许浓度 10mg/m3,对人体健康的危害主要是通过呼吸道吸入或皮肤侵入。我国对环境大气、车间空气及工业废气中的硫化氢浓度已有严格的规定。居民区环境大气中硫化氢的浓度最高不得超过0.01mg/m3;国家规定的环境恶臭污染物控制标准中硫化氢的厂界一级标准值为小于0.03mg/m3;车间工作地点空气中硫化氢的浓度最高不得超过10mg/m3;城市煤气中硫化氢的浓度不得超过20mg/m3;油品炼厂废气中硫化氢的浓度要求净化至10~20mg/m3。硫化氢是强烈的神经毒物,当高浓度时可直接抑制呼吸中枢,引起迅速窒息而致死亡。随着人类对环境的要求越来越严格,对排气中硫化物浓度也提出了更严格的要求,因此, 硫化氢去除问题日显突出。
目前,国内外越来越重视去除H2S方法的研究。处理H2S的传统方法主要有三种,物理法只适宜处理低浓度、范围小的恶臭,且成本较高;化学法除臭不持久,除臭设施投资和运行费用高;生物法虽成本低廉,效果好,但菌种的筛选培养较为困难,见效稍慢。光催化氧化反应是一种高级的氧化过程(Advanced Oxidation process,简称AOP),与传统方法相比较,由于光催化方法反应条件温和、能耗低、无二次污染、可以在常温常压下氧化分解结构稳定的化合物、材料本身在反应过程中并不消耗、在正常气压下操作、可重复使用等优点,光催化技术逐渐成为备受瞩目的一种恶臭气体治理方法。
光催化氧化去除H2S的核心关键是开发有效的光催化剂。中国专利CN106732818A公开了一种TiO2@MIL-100双层中空材料对硫化氢气体有着很好的光催化效果,但其材料的合成分三步进行,且需要聚苯乙烯纳米球为模板,高温煅烧等苛刻条件;中国专利CN101927173A公开了一种原子比为Zn : Cd =7:3的光催化剂ZnIn2S4-CdIn2S4在高压汞灯光照下可以光催化分解硫化氢,众所周知,高压汞灯光源存在高耗能、危险性高等缺点;中国专利CN102671537A公开了锐钛矿型的改性负载光催化剂ACF/Fe/Ce/TiO2可以将低浓度的硫化氢气体在光催化反应器中15~30w紫外灯下进行吸附光解,但其应用局限于低浓度(1ppm)的H2S气体吸附光解;中国专利CN101760272A公开了TiO2负载在过渡金属改性MCM-41分子筛表面制得催化剂在可见光下将空气和沼气的混合气通入到光催化反应器中,将混合气中的硫化氢光催化氧化为硫酸盐沉积在催化床上,此方法只是将硫化氢转换为硫酸盐沉积,未能在光降解H2S的同时产生氢气等能源气体;中国专利CN101623646公开了一种丝光沸石负载型CdS光催化剂可以可见光分解硫化氢;中国专利CN101293632公开了一种贵金属担载的Cd1-yZnyS光催化剂在可见光下分解硫化氢, 但以上两种材料都属于硫化物,其本身在光催化应用中都存在着易光腐蚀,催化剂不稳定等缺点,此外催化剂中所含Cd元素属于重金属,毒性大,对于人体以及环境都有较大伤害,并不适合大规模投入使用。
发明内容
针对现有技术的不足,本发明的目的在于提供一种WO3·H2O纳米片自组装的微米球的光催化材料的制备方法,用于去除硫化氢气体,其光催化效率高,合成方法简单易行,安全低耗,无毒无害,绿色环保,可大规模使用。
为达此目的,本发明采用以下技术方案 :
一种基于纳米片自组装成微米球WO3·H2O材料的制备方法,包括以下步骤:
1)将Na2WO4·2H2O溶于去离子水中,充分搅拌使之完全溶解。
2)将一定量的全氟丁基磺酸钾加入步骤1)所得溶液中,搅拌5-30min。
3)将一定量的柠檬酸加入步骤2)所得溶液中,搅拌5-60min。
4)将一定量的盐酸溶液逐滴加入到步骤3)所得溶液中,于室温下充分搅拌0.5-1h。
5)将上述步骤所得溶液转移至100ml反应釜中,在一定温度下水热反应一段时间,将所得沉淀产物进行离心、洗涤、烘干,得到由纳米片自组装的微米球的WO3·H2O。
按上述方案,步骤1)所述的Na2WO4·2H2O为0.25-2mmol。
按上述方案,步骤2)所述的全氟丁基磺酸钾为0-5mmol。
按上述方案,步骤3)所述的柠檬酸为1-10mmol。
按上述方案,步骤4)所述的盐酸浓度为1-5mol/L,加入量为1-10mL。
按上述方案, 步骤 5) 所述的水热反应温度为60-150℃,水热反应时间为4-50h。
本发明提出在表面活性剂(全氟丁基磺酸钾)和柠檬酸的作用下,在一步水热反应中WO3·H2O结晶形成纳米片,进而自发组装为微米球。
WO3·H2O纳米片自组装微米球的光催化材料的光催化活性是通过在紫外灯照射下对硫化氢气体进行吸附光解来进行测试的。
WO3· H2O纳米片自组装微米球的光催化材料的物理性能表征方法:用X射线衍射(XRD)光谱分析产物物质组成及结构情况,用场发射扫描电镜(FESEM)观察产物的形貌。
本发明的优点在于:本发明所述的纳米片自组装微米球的WO3·H2O光催化材料的制备方法简便易行,水热反应条件温和,不需高温、高压、强酸等苛刻的合成条件,通过一步水热即可得到形貌均匀的WO3·H2O纳米片自组装微米球光催化材料。
与现有技术相比,本发明的有益效果为:
本发明通过简单的一步水热法制备的WO3·H2O纳米片自组装微米球光催化材料,形貌均一,性能稳定,用于硫化氢气体降解,光催化效率高,催化剂在254nm光照下均具有良好的光催化降解硫化氢的效果,紫外可见光吸收性能好,适合广泛应用于有毒及污染化学物质降解及洗消领域。
附图说明
图1为实例1合成方法所制得产物的XRD谱图。
图2为实例1合成方法所制得产物的SEM照片。
图3为实例1所得催化剂的光催化分解硫化氢气体两次循环实验的效果图。
图4为实例1光催化分解硫化氢气体实验装置示意图。
附图标记如下:
1-支架;2-氨浓度监测仪;3-流量计;4-风扇;5-紫外灯;6-催化剂;7-硫化氢钢瓶。
具体实施方式
下面结合实施例进一步说明本发明,该实例只用于说明本发明,并不限制本发明。
实施例一
纳米球的制备,具体步骤如下:
将0.5mmol Na2WO4·2H2O加入至70mL 去离子水中,搅拌至溶解,再加入0.5mmol 全氟丁基磺酸钾,搅拌5min 后加入2mmol 柠檬酸,使混合溶液充分搅拌15min后缓慢滴入5mL3mol/L的盐酸溶液,于室温下充分搅拌30min,随后将其移入100mL聚四氟乙烯内村,密封置于高压反应釜钢套中,于烘箱中恒温100℃保持8小时,水热结束使其自然降温。将合成好的样品,用去离子水和乙醇离心洗涤3次,将得到的催化剂60℃恒温干燥10h,充分研磨即得催化剂。用这种方法合成的催化剂具有较高的结晶度,且与WO3·H2O标准卡片PDF#43-0679完全吻合(如图1)。其形貌均一,是由50-100nm厚度的纳米片组装而成的微米球,直径约为2-3μm。
实施例二
硫化氢气体的光催化降解实验,具体步骤如下:
本发明的光催化降解硫化氢气体性能实验中的实验装置如图4所示。光催化实验测试在25℃温度,50%RH湿度下的环境测试舱内进行,环境测试舱内的尺寸为3立方米。光催化实验装置的测试舱内包括从上至下依次设置的风扇4、紫外灯5、催化剂6、支架1,所述光催化装置的一端连接有硫化氢气体钢瓶,另一端与所述硫化氢浓度监测仪2连接,其中,硫化氢气体流量通过流量计3控制,通入硫化氢的量为80mL/min,90s催化剂的用量为3g,以分散粉体的形式喷撒在面积为15cm*35cm的玻璃纤维载体上,厚度为1.0 mm。所用光源为直型波长254nm紫外灯。硫化氢的流量采用北京七星华创电子股份有限公司生产的D07系列型硫化氢气体流量计控制。硫化氢的浓度测试采用东莞市威拓仪器有限公司生产的HYCA-1硫化氢检测仪,检测限为:0-100ppm,灵敏度为0.01ppm。
实验过程:调节测试舱的温度为25℃,湿度为50%RH,关闭测试舱与外界联通的阀门,使之成为一个密闭体系,往测试舱内注入硫化氢,控制在6ppm左右,再进行相应的测试。
在图4的光催化反应装置中的两次循环实验结果如图3所示,经过四个小时的光催化反应,舱内H2S的浓度可由5.25ppm降低至0ppm附近,显示出较为突出的光催化降解H2S性能,并且经过两次循环实验,降解效果基本保持不变,可见本发明的催化剂具备高效且稳定的光催化降解H2S的效果。
Claims (4)
1.一种用于去除异味硫化氢的WO3·H2O纳米片自组装微米球光催化材料的制备方法,其特征在于:包括以下依次步骤:
1)将一定量的Na2WO4·2H2O溶于去离子水中,充分搅拌使之溶解;
2)将一定量的全氟丁基磺酸钾在搅拌下加入步骤1)所得溶液中,继续搅拌;
3)向步骤2)所得溶液中加入一定量的柠檬酸,然后充分搅拌;
4)将步骤3)中所得溶液中加入一定量稀盐酸,然后搅拌0.5-1 h;
5)将步骤4)所得浊液转移至100 mL反应釜中,在一定温度下水热反应一段时间,所得沉淀物经离心、洗涤、干燥,得到WO3·H2O纳米片自组装微米球。
2.根据权利要求1所述的WO3·H2O纳米片自组装微米球光催化材料的制备方法,其特征在于:所述Na2WO4·2H2O 为0.25-2 mmol,全氟丁基磺酸钾为0-5 mmol,柠檬酸为1-10mmol,去离子水为70 mL。
3.根据权利要求1所述的WO3·H2O纳米片自组装微米球光催化材料的制备方法,其特征在于:步骤4)所述稀盐酸浓度为1-5mol/L,加入量为1-10mL。
4.根据权利要求1所述的WO3·H2O纳米片自组装微米球光催化材料的制备方法,其特征在于:步骤5)所述水热反应温度为60-150 ℃,反应时间为4-24 h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811539341.0A CN109647378B (zh) | 2018-12-17 | 2018-12-17 | 一种用于去除异味硫化氢的纳米片自组装微米球光催化材料的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811539341.0A CN109647378B (zh) | 2018-12-17 | 2018-12-17 | 一种用于去除异味硫化氢的纳米片自组装微米球光催化材料的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109647378A true CN109647378A (zh) | 2019-04-19 |
CN109647378B CN109647378B (zh) | 2021-08-31 |
Family
ID=66113533
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811539341.0A Active CN109647378B (zh) | 2018-12-17 | 2018-12-17 | 一种用于去除异味硫化氢的纳米片自组装微米球光催化材料的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109647378B (zh) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101318704A (zh) * | 2008-07-08 | 2008-12-10 | 清华大学 | 一种氧化钨纳米线及氧化钨纳米线气敏传感器的制备方法 |
CN101318705A (zh) * | 2007-06-08 | 2008-12-10 | 郑州大学 | 一种取向三氧化钨纳米薄膜的制备方法 |
CN102408095A (zh) * | 2011-08-20 | 2012-04-11 | 大连理工大学 | 一种分解硫化氢制备氢气和单质硫的方法 |
CN103787418A (zh) * | 2014-01-21 | 2014-05-14 | 中国科学院金属研究所 | 一种制备纳米片组装的wo3·h2o空心球的方法 |
CN105842291A (zh) * | 2016-03-28 | 2016-08-10 | 福州大学 | 一种CuWO4/WO3复合光助气敏元件及其制备方法 |
CN105836807A (zh) * | 2016-06-01 | 2016-08-10 | 武汉工程大学 | 一种二维薄片自组装多级结构氧化钨及其制备方法和应用 |
CN105854870A (zh) * | 2016-05-11 | 2016-08-17 | 福州大学 | 一种Bi2WO6分级凹槽微米球光催化剂及其制备方法 |
CN106430312A (zh) * | 2016-09-18 | 2017-02-22 | 江苏理工学院 | 一种单斜晶系三氧化钨的制备方法 |
CN106745275A (zh) * | 2017-01-24 | 2017-05-31 | 南昌大学 | 一种一水合三氧化钨纳米片的制备方法 |
KR20180003881A (ko) * | 2016-07-01 | 2018-01-10 | 전남대학교산학협력단 | 3d 프린팅용 복합재료, 이를 이용한 전자부품의 제조방법 |
US10105687B1 (en) * | 2017-08-24 | 2018-10-23 | Imam Abdulrahman Bin Faisal University | Heterostructured Bi2S3—ZnS photocatalysts and methods thereof |
-
2018
- 2018-12-17 CN CN201811539341.0A patent/CN109647378B/zh active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101318705A (zh) * | 2007-06-08 | 2008-12-10 | 郑州大学 | 一种取向三氧化钨纳米薄膜的制备方法 |
CN101318704A (zh) * | 2008-07-08 | 2008-12-10 | 清华大学 | 一种氧化钨纳米线及氧化钨纳米线气敏传感器的制备方法 |
CN102408095A (zh) * | 2011-08-20 | 2012-04-11 | 大连理工大学 | 一种分解硫化氢制备氢气和单质硫的方法 |
CN103787418A (zh) * | 2014-01-21 | 2014-05-14 | 中国科学院金属研究所 | 一种制备纳米片组装的wo3·h2o空心球的方法 |
CN105842291A (zh) * | 2016-03-28 | 2016-08-10 | 福州大学 | 一种CuWO4/WO3复合光助气敏元件及其制备方法 |
CN105854870A (zh) * | 2016-05-11 | 2016-08-17 | 福州大学 | 一种Bi2WO6分级凹槽微米球光催化剂及其制备方法 |
CN105836807A (zh) * | 2016-06-01 | 2016-08-10 | 武汉工程大学 | 一种二维薄片自组装多级结构氧化钨及其制备方法和应用 |
KR20180003881A (ko) * | 2016-07-01 | 2018-01-10 | 전남대학교산학협력단 | 3d 프린팅용 복합재료, 이를 이용한 전자부품의 제조방법 |
CN106430312A (zh) * | 2016-09-18 | 2017-02-22 | 江苏理工学院 | 一种单斜晶系三氧化钨的制备方法 |
CN106745275A (zh) * | 2017-01-24 | 2017-05-31 | 南昌大学 | 一种一水合三氧化钨纳米片的制备方法 |
US10105687B1 (en) * | 2017-08-24 | 2018-10-23 | Imam Abdulrahman Bin Faisal University | Heterostructured Bi2S3—ZnS photocatalysts and methods thereof |
Non-Patent Citations (2)
Title |
---|
XINGANG WANG ET AL.: "Controlled morphologies and growth direction of WO3 nanostructures hydrothermally synthesized with citric acid", 《MATERIALSLETTERS》 * |
张婧等: "硫化氢直接分解制取氢气和硫黄研究进展", 《化工进展》 * |
Also Published As
Publication number | Publication date |
---|---|
CN109647378B (zh) | 2021-08-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103030179B (zh) | 水热法制备三氧化钨纳米片及其应用 | |
CN109261172A (zh) | 一种碘氧化铋/溴氧化铋异质结光催化剂的制备方法和用途 | |
Chen et al. | CTAB-assisted synthesis of Bi2MoO6 hierarchical microsphere and its application as a novel efficient and recyclable adsorbent in removing organic pollutants | |
CN107486198B (zh) | 一种基于桃花生物质碳修饰的Bi2WO6复合光催化剂的制备方法及用途 | |
CN100453167C (zh) | 以植物皮、膜为模板制备介孔二氧化钛光催化剂的方法 | |
CN107362805B (zh) | 一种基于生物质炭的磁性氧化铋复合光催化剂的制备方法及用途 | |
CN108126718B (zh) | 一种In2S3/BiPO4异质结光催化剂的制备方法及其应用 | |
Palas et al. | Bioinspired metal oxide particles as efficient wet air oxidation and photocatalytic oxidation catalysts for the degradation of acetaminophen in aqueous phase | |
CN105363433A (zh) | 石墨烯基钨酸铋复合光催化剂及其制备方法和应用 | |
CN104258885A (zh) | 一种片状羟基磷酸铜纳米材料的制备方法 | |
CN111545246A (zh) | 一种纳米复合光催化剂AgCl/ZIF-8的制备方法及由此制得的纳米复合光催化剂 | |
CN106390971A (zh) | 一种生物炭基二氧化钛光催化材料的制作方法 | |
CN102030358B (zh) | 多孔氧化锌纳米棒及其制备方法 | |
CN109911936A (zh) | 一种片状碱式硝酸铋及其制备方法 | |
Ma et al. | Photocatalytic degradation of octadecylamine and 4-dodecylmorpholine over titanium based photocatalyst: Activity and mechanism insights | |
CN105883915A (zh) | 一种纳米晶二氧化钛微球及其作为臭氧氧化催化剂的应用 | |
CN108043390A (zh) | 纳米片Bi2WO6/SnO2催化降解液相污染物的方法 | |
CN109046433A (zh) | g-C3N4/BiOBr光催化降解卡马西平的方法 | |
CN108855080A (zh) | 一种中空结构生物质炭/TiO2多壁管/CuO光催化剂及其制备方法 | |
CN106219666B (zh) | 一种Pt掺杂In2O3光催化降解水中PFOA的方法 | |
CN109647378A (zh) | 一种用于去除异味硫化氢的纳米片自组装微米球光催化材料的制备方法 | |
CN111036240A (zh) | 一种MoS2/CuO异质结光催化剂及其制备方法和应用 | |
CN104445415A (zh) | 一种新型Bi3.84W0.16O6.24纳米材料及其制备方法和应用 | |
CN101234342A (zh) | 一种高效的二氧化钛基纳米复合材料光催化剂及其制备方法 | |
CN103769189A (zh) | 一种碳氮共掺杂{001}面暴露的纳米二氧化钛的制备方法 |
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 |