CN110237853B - 一种铬酸钆/银/磷酸银复合物光催化剂及其在VOCs净化中的应用 - Google Patents
一种铬酸钆/银/磷酸银复合物光催化剂及其在VOCs净化中的应用 Download PDFInfo
- Publication number
- CN110237853B CN110237853B CN201910615439.8A CN201910615439A CN110237853B CN 110237853 B CN110237853 B CN 110237853B CN 201910615439 A CN201910615439 A CN 201910615439A CN 110237853 B CN110237853 B CN 110237853B
- Authority
- CN
- China
- Prior art keywords
- gadolinium
- chromate
- silver
- silver phosphate
- phosphate
- 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.)
- Active
Links
- OFNHMKFJXLGYNW-UHFFFAOYSA-N dioxido(dioxo)chromium gadolinium(3+) Chemical compound [Cr](=O)(=O)([O-])[O-].[Gd+3].[Cr](=O)(=O)([O-])[O-].[Cr](=O)(=O)([O-])[O-].[Gd+3] OFNHMKFJXLGYNW-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910000161 silver phosphate Inorganic materials 0.000 title claims abstract description 61
- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 51
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- 238000000746 purification Methods 0.000 title claims abstract description 7
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 silver phosphate compound Chemical class 0.000 claims abstract description 16
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 15
- 229940100890 silver compound Drugs 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 9
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000008096 xylene Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910001316 Ag alloy Inorganic materials 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 abstract 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 14
- 229910001961 silver nitrate Inorganic materials 0.000 description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- JAOZQVJVXQKQAD-UHFFFAOYSA-K gadolinium(3+);phosphate Chemical compound [Gd+3].[O-]P([O-])([O-])=O JAOZQVJVXQKQAD-UHFFFAOYSA-K 0.000 description 1
- RQXZRSYWGRRGCD-UHFFFAOYSA-H gadolinium(3+);tricarbonate Chemical compound [Gd+3].[Gd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O RQXZRSYWGRRGCD-UHFFFAOYSA-H 0.000 description 1
- QLAFITOLRQQGTE-UHFFFAOYSA-H gadolinium(3+);trisulfate Chemical compound [Gd+3].[Gd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QLAFITOLRQQGTE-UHFFFAOYSA-H 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- HTRJDXQPCKIFIU-UHFFFAOYSA-N silver;ethanol;nitrate Chemical compound [Ag+].CCO.[O-][N+]([O-])=O HTRJDXQPCKIFIU-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种铬酸钆/银/磷酸银复合物光催化剂及其在VOCs净化中的应用，该复合物的表述方式为GdCrO3/Ag/Ag3PO4。制备方法如下：1）按照1:1的比例取钆源和铬源于研钵中，加入适量的尿素，研磨均匀后置于特定气氛中高温中焙烧，得到铬酸钆；2）在铬酸钆上负载银颗粒，得铬酸钆/银复合物；3）在铬酸钆/银上负载磷酸银，得到铬酸钆/银/磷酸银复合物。本发明制得的GdCrO3/Ag/Ag3PO4中的单质Ag在可见光激发下发生等离子共振而产生热电子‑空穴对。热电子‑空穴对连接了能隙分离的半导体GdCrO3和Ag3PO4而不牺牲它们的氧化或还原电位，从而强化了复合物的光催化氧化还原能力。GdCrO3/Ag/Ag3PO4被用于光催化降解有机污染物。它在可见光照射及温和反应条件下，如90oC，完全催化净化甲苯、二甲苯和苯等典型有机气体污染物。
Description
技术领域
本发明涉及一种铬酸钆/银/磷酸银复合物光催化剂及其在VOCs净化中的应用，属于光催化材料和环境保护技术领域。
背景技术
光催化降解污染物技术具有条件温和反应能耗低等特点，是最有应用前景的技术之一。但传统光催化剂，如TiO2，存在光生电子-空穴对的快速复合、量子产量低和净化效率低等问题。复合物异质体系的构建被认为是降低光生电子-空穴对复合率的有效方法，例如通过构建Z型异质结In2O3-Ag-Ag3PO4（Chemical Engineering Journal,2017, 320, 644-652.），或传统II型异质结Ag2S/Ag3PO4 （Applied Catalysis B: Environmental, 2017,209, 566-578.）都能提升Ag3PO4上光生电子-空穴对的分离效率。然而，这些现有异质体系构建思路和技术普遍存在牺牲其组成单体原有的氧化或还原电位的情况，未能有效提升光催化净化有机污染物的性能。
发明内容
针对以上光催化领域中复合物异质体系所面临的问题，本发明提供了一种铬酸钆/银/磷酸银复合物光催化剂(GdCrO3/Ag/Ag3PO4)及其制备方法和应用。所述复合物催化剂中，以催化剂的重量为100%计，单质Ag的重量分数为0.1%~20%，磷酸银的重量分数为1%~40.0%。所述复合物中的单质Ag在可见光激发下发生等离子共振作用产生热电子-空穴对以接收Ag3PO4产生的光生电子，并将其传递到GdCrO3的光生空穴上，将能隙分离的GdCrO3和Ag3PO4连接起来并充分利用了各自的氧化或还原电位，制备高效GdCrO3/Ag/Ag3PO4复合物光催化材料。
上述的铬酸钆/银/磷酸银复合物光催化剂的制备方法，包括以下步骤：
（1）按照1:1的比例取钆源和铬源于研钵中，加入适量的尿素，研磨均匀后置于特定气氛中高温焙烧，得到铬酸钆；
（2）在铬酸钆上负载银颗粒，得铬酸钆/银复合物；
（3）在铬酸钆/银上负载磷酸银，得到铬酸钆/银/磷酸银复合物。
其中，步骤（1）的钆源可选用硝酸钆、氯化钆、磷酸钆、碳酸钆、硫酸钆等, 优选硝酸钆；铬源可选用硝酸铬、氯化铬、磷酸铬、碳酸铬、硫酸铬等，优选硝酸铬。焙烧气氛为空气，也可以氧气与惰性气体组成的不同比例的混合气体代替，煅烧温度为150~1100 oC，焙烧时间为0.1~24 h。优选焙烧温度为700~900 oC，焙烧时间为3~6 h。
步骤（2）中，银源可为硝酸银，氯化银，磷酸银，硫酸银等，优选硝酸银并配成前驱体溶液。采用液相还原法，选用葡萄糖溶液作为还原剂，将银还原负载在铬酸钆上。亦可选用NaBH4或其它还原剂，或选用光照还原法、煅烧还原法等其它还原方法将Ag颗粒负载到铬酸钆上。
步骤（3）中的磷酸银复合铬酸钆/银的方法为液相沉积法。选用磷酸氢二钠水溶液和硝酸银水溶液作为前驱体溶液，在铬酸钆/银上液相反应沉积磷酸银。亦可选用固相研磨复合法在银/铬酸钆上复合磷酸银。
用焙烧法制备钙钛矿结构的GdCrO3已有公开报道，如Hou等（Applied Catalysis B: Environmental,2018, 232, 124-134.）报道了焙烧法制备纯相GdCrO3的方法。在液相还原法中，葡萄糖作为还原剂还原银离子制单质银也已有公开报道，如Bi等（Chemistry-A European Journal, 2012, 18, 14272-14275.）用葡萄糖溶液在立方体型的Ag3PO4上选择性的还原制备单质银。上述的焙烧和液相还原法也是本领域人员常用实验条件。但本发明通过精确控制复合物材料组分的比例、银源的加入量与还原条件、磷酸根原位部分腐蚀铬酸钆/银及磷酸银原位沉积等工序首次得到了铬酸钆/银/磷酸银复合物。
本发明的再一个目的是提供铬酸钆/银/磷酸银复合物的应用。
本发明所提供的铬酸钆/银/磷酸银复合物的应用是其在光催化降解空气中挥发性有机气体污染物（或VOCs）中的应用，如甲苯、二甲苯、苯等气体污染物。
与现有技术相比，本发明具有如下优点和有益效果：（1）铬酸钆/银/磷酸银复合物的制备工艺简单，实验周期短，除了铬酸钆涉及高温合成，其余步骤均可在室温下进行，便于工业放大生产。（2）本发明制备得到的铬酸钆/银/磷酸银复合物能在可见光照射及温和反应条件下，如90 oC，完全催化净化甲苯、二甲苯和苯等典型VOCs。
具体实施方式
下面结合具体的实施例对本发明作进一步详细的叙述，但本发明的实施方法灵活，不仅仅限于此例所述的具体操作方式，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
实施例1
一种铬酸钆/银/磷酸银复合物光催化剂：（1）称取摩尔比为1:1的硝酸钆和硝酸铬于含有适量尿素的研钵中研磨均匀后转移到马弗炉中空气气氛下850 ℃焙烧3 h，得到铬酸钆；（2）将0.6 g铬酸钆加入由30 mL 42.47 g/L硝酸银水溶液与0.5mol/L的稀氨水配制的银氨溶液中搅拌30 min后再加入20 mL 的297.25 g/L的葡萄糖水溶液，并继续搅拌5min得铬酸钆/银复合物；（3）将0.3 g铬酸钆/银复合物加入30 mL的 9.47 g/L的磷酸氢二钠水溶液中搅拌30 min后再滴加15 mL 的5.67 g/L硝酸银水溶液,并继续搅拌30 min后得到铬酸钆/银/磷酸银复合物，以催化剂的重量为100%，单质Ag的质量分数为4.2%，磷酸银的质量分数为25.9%。
对比例1
对比一种铬酸钆/银/磷酸银复合物光催化剂。将0.3 g实施例1中的铬酸钆加入30mL的 9.47 g/L的磷酸氢二钠水溶液中搅拌30 min后，再滴加入30 mL的 5.67 g/L硝酸银水溶液，并继续搅拌30 min后得铬酸钆/磷酸银复合物。
对比例2
对比一种铬酸钆/银/磷酸银复合物光催化剂。称取摩尔比为1:1的硝酸钆和硝酸铬于含有适量尿素的研钵中研磨均匀后转移到马弗炉中空气气氛下850 ℃焙烧3 h，得到铬酸钆；（2）将0.6 g铬酸钆加入由30 mL 的42.47 g/L硝酸银水溶液与0.5 mol/L的稀氨水配制的银氨溶液中搅拌30 min后再加入20 mL的 297.25 g/L的葡萄糖水溶液，并继续搅拌5 min得铬酸钆/银复合物。
对比例3
对比一种铬酸钆/银/磷酸银复合物光催化剂。（1）将30 mL的 14.2 g/L磷酸氢二钠水溶液滴加入30 mL的 42.47 g/L硝酸银水溶液中，搅拌30 min得磷酸银；（2）将0.3 g磷酸银加入由30 mL的 21.23 g/L硝酸银水溶液和0.5 mol/L的稀氨水配制的银氨溶液中搅拌30 min后再加入20 mL 的148.63 g/L的葡萄糖水溶液，并继续搅拌5 min得磷酸银/银复合物。
实施例2
一种铬酸钆/银/磷酸银复合物光催化剂：（1）称取摩尔比为1:1的硝酸钆和硝酸铬于含有适量尿素的研钵中研磨均匀后转移到马弗炉中空气气氛下700 ℃焙烧6 h，得到铬酸钆；（2）将0.6 g铬酸钆加入由30 mL的 15.0 g/L硝酸银水溶液搅拌30 min后再加入10mL的 5.0 g/L的NaBH4水溶液，并继续搅拌10 min得铬酸钆/银复合物；（3）将0.3 g铬酸钆/银复合物与0.05 g磷酸银混研磨均匀合,在氮气氛围中500 oC煅烧2 h得到铬酸钆/银/磷酸银复合物，以催化剂的重量为100%，单质Ag的质量分数为11.1%，磷酸银的质量分数为14.3%。
实施例3
一种铬酸钆/银/磷酸银复合物光催化剂：（1）称取摩尔比为1:1的硝酸钆和硝酸铬于含有适量尿素的研钵中研磨均匀后转移到马弗炉中空气气氛下800 ℃焙烧4.5 h，得到铬酸钆；（2）将0.6 g铬酸钆加入由30 mL的 24.0 g/L硝酸银水乙醇混合溶液，在Xe灯下光照30 min后得铬酸钆/银复合物；（3）将0.3 g铬酸钆/银复合物加入30 mL的14.21 g/L的磷酸氢二钠水溶液中搅拌30 min后滴加15 mL的8.51 g/L硝酸银水溶液,并继续搅拌30 min后得到铬酸钆/银/磷酸银复合物，以催化剂的重量为100%，单质Ag的质量分数为0.4%，磷酸银的质量分数为33.3%。
实施例4
一种铬酸钆/银/磷酸银复合物光催化剂及其制备方法：（1）称取摩尔比为1:1的硝酸钆和硝酸铬于含有适量尿素的研钵中研磨均匀后转移到马弗炉中空气气氛下900 ℃煅烧2 h，得到铬酸钆；（2）将0.6 g铬酸钆加入由30 mL的30.0 g/L硝酸银乙醇水溶液会发干后，于500 oC下空气煅烧2 h还原得铬酸钆/银复合物；（3）将0.3 g铬酸钆/银复合物加入30mL的18.94 g/L的磷酸氢二钠水溶液中搅拌30 min后滴加15 mL的11.34 g/L硝酸银水溶液,并继续搅拌30 min后得到铬酸钆/银/磷酸银复合物，以催化剂的重量为100%，单质Ag的质量分数为12.3%，磷酸银的质量分数为40.0%。
分别取0.2 g实施例1-4和对比例1-3所述催化剂，均匀涂膜在7.0 cm2的表面皿上，并置于反应釜底部，用混合气（O2:N2=1:3）吹扫30 min除去反应釜内CO2。甲苯、二甲苯或苯可见光催化反应实验条件：甲苯气体通过鼓泡，由混合气（O2:N2=1:3）吹入反应釜，二甲苯和苯由移液枪从反应器外加入。甲苯、二甲苯或苯在反应釜中的初始浓度都为~700 ppm，光照前反应釜在室温下避光处理30 min，使甲苯、二甲苯或苯在催化剂表面达到吸附-脱附平衡。装上UVIR-cut400滤波片的300 W的氙灯作为模拟可见光源(λ=400~780 nm，光强为100mw·cm-2)，在90 oC条件下反应2 h，通过气相色谱（GC7900, FID）检测甲苯、二甲苯或苯浓度和气相色谱(GC2060, FID）检测CO2产量并用于换算甲苯、二甲苯或苯的消除率。
表1铬酸钆/银/磷酸银复合物光催化剂可见光照射下活性评价结果
Claims (6)
1.一种铬酸钆/银/磷酸银复合物光催化剂，其特征在于：以催化剂的重量为100％，单质银的重量分数为0.1％～20％,磷酸银的重量分数为1％～40.0％。
2.如权利要求1所述铬酸钆/银/磷酸银复合物光催化剂的制备方法，其特征在于：包括以下步骤：
(1)按照1:1的比例取硝酸钆和硝酸铬于研钵中，加入适量的尿素，研磨均匀后置于含氧气氛中高温焙烧，得到铬酸钆；
(2)在铬酸钆上负载银颗粒，得铬酸钆/银复合物；
(3)在铬酸钆/银上负载磷酸银，得到铬酸钆/银/磷酸银复合物。
3.根据权利要求2中所述的制备方法，其特征在于，步骤(1)中的焙烧温度为700～1100℃，煅烧为2～24h。
4.根据权利要求2所述的制备方法，其特征在于，步骤(2)中采用液相还原法、光照还原法或气相还原法将银离子还原负载到铬酸钆上。
5.根据权利要求2所述的制备方法，其特征在于，步骤(3)中所述的在铬酸钆/银上负载磷酸银的方法为液相沉积法或固相研磨复合法。
6.如权利要求1所述铬酸钆/银/磷酸银复合物光催化剂或权利要求2～5任一项所述制备方法制备的铬酸钆/银/磷酸银复合物光催化剂在VOCs净化中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910615439.8A CN110237853B (zh) | 2019-07-09 | 2019-07-09 | 一种铬酸钆/银/磷酸银复合物光催化剂及其在VOCs净化中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910615439.8A CN110237853B (zh) | 2019-07-09 | 2019-07-09 | 一种铬酸钆/银/磷酸银复合物光催化剂及其在VOCs净化中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110237853A CN110237853A (zh) | 2019-09-17 |
| CN110237853B true CN110237853B (zh) | 2022-07-05 |
Family
ID=67891577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910615439.8A Active CN110237853B (zh) | 2019-07-09 | 2019-07-09 | 一种铬酸钆/银/磷酸银复合物光催化剂及其在VOCs净化中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110237853B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659392B (zh) * | 2020-06-17 | 2023-11-28 | 中山大学 | 一种由氧化钨-金属表面等离子共振激元-铬酸钆组成的桥式异质催化剂的制备及应用 |
| CN112264060A (zh) * | 2020-10-22 | 2021-01-26 | 盐城工学院 | 一种Ag3PO4-Bi2WO6可见光催化剂的制备方法和应用 |
| CN113663689B (zh) * | 2021-06-25 | 2024-03-15 | 中山大学 | 一种用于净化空气中甲醛污染物的光热催化炭材料 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258886A (zh) * | 2014-09-16 | 2015-01-07 | 上海电力学院 | 一种磷酸银/氧缺陷型二氧化钛复合光催化剂及制备方法 |
| CN108579775A (zh) * | 2018-05-15 | 2018-09-28 | 浙江大学城市学院 | 一种磷酸银/银/二氧化钛纳米花复合材料及其制备方法与应用 |
| CN109126836A (zh) * | 2018-09-28 | 2019-01-04 | 陕西科技大学 | 一种溴化银/铬酸银n-n异质结复合光催化剂的制备方法 |
| CN109277106A (zh) * | 2018-09-17 | 2019-01-29 | 安徽建筑大学 | 一种Ag/Ag3PO4/硅藻土复合可见光光催化剂及其制备方法 |
| CN109289884A (zh) * | 2018-11-30 | 2019-02-01 | 太原理工大学 | 一种银-磷酸银-三氧化钨三元复合纳米光催化材料及其制备方法和应用 |
-
2019
- 2019-07-09 CN CN201910615439.8A patent/CN110237853B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258886A (zh) * | 2014-09-16 | 2015-01-07 | 上海电力学院 | 一种磷酸银/氧缺陷型二氧化钛复合光催化剂及制备方法 |
| CN108579775A (zh) * | 2018-05-15 | 2018-09-28 | 浙江大学城市学院 | 一种磷酸银/银/二氧化钛纳米花复合材料及其制备方法与应用 |
| CN109277106A (zh) * | 2018-09-17 | 2019-01-29 | 安徽建筑大学 | 一种Ag/Ag3PO4/硅藻土复合可见光光催化剂及其制备方法 |
| CN109126836A (zh) * | 2018-09-28 | 2019-01-04 | 陕西科技大学 | 一种溴化银/铬酸银n-n异质结复合光催化剂的制备方法 |
| CN109289884A (zh) * | 2018-11-30 | 2019-02-01 | 太原理工大学 | 一种银-磷酸银-三氧化钨三元复合纳米光催化材料及其制备方法和应用 |
Non-Patent Citations (2)
| Title |
|---|
| Novel Pd/GdCrO3 composite for photo-catalytic reduction of nitrate to N2 with high selectivity and activity;Zhiang Hou et al.;《Applied Catalysis B: Environmental》;20180319;第232卷;第124-126页 * |
| Z-scheme Ag3PO4/Ag/SrTiO3 Heterojunction for Visible-Light Induced Photothermal Synergistic VOCs Degradation with Enhanced Performance;Weikang Ji et al.;《Ind. Eng. Chem. Res.》;20190705;第58卷;第13951，13953和13957页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110237853A (zh) | 2019-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110368924B (zh) | 一种钛酸铋/铋/钒酸铋复合物光催化剂及其在光热催化净化有机气体污染物中的应用 | |
| US20220042184A1 (en) | Preparation Method and Application of Non-noble Metal Single Atom Catalyst | |
| CN110237853B (zh) | 一种铬酸钆/银/磷酸银复合物光催化剂及其在VOCs净化中的应用 | |
| JP4803414B2 (ja) | 新規ｚ−スキーム型可視光活性な水の完全分解用光触媒系及び前記触媒を用いた水の完全分解方法 | |
| CN112169819A (zh) | 一种g-C3N4 (101)-(001)-TiO2复合材料的制备方法和应用 | |
| CN104646001B (zh) | 一种可见光响应型铁酸铋‑氧化铋复合材料及其制备方法 | |
| CN102500358A (zh) | 一种具有良好抗碱金属和碱土金属中毒性能的脱硝催化剂 | |
| Yang et al. | Reaction mechanism and selectivity regulation of photocatalytic nitrate reduction for wastewater purification: progress and challenges | |
| WO2019223051A1 (zh) | 光催化电极耦合微生物燃料电池促进焦化废水处理方法 | |
| CN109174144B (zh) | Ni3C@Ni核壳助催化剂和Ni3C@Ni/光催化剂复合材料及其制备方法与应用 | |
| CN111659392B (zh) | 一种由氧化钨-金属表面等离子共振激元-铬酸钆组成的桥式异质催化剂的制备及应用 | |
| CN111408413A (zh) | 一种改性氮化碳/Fe基MOF复合材料及其制备方法和应用 | |
| CN111185204B (zh) | 一种可见光催化剂及其制备方法与应用 | |
| CN109317184A (zh) | 双功能β-FeOOH/eg-C3N4复合纳米材料及其制备方法和应用 | |
| He et al. | Synergistic reduction of U (VI) and selective oxidation of benzyl alcohol to prepare benzaldehyde via WOx/g-C3N4 | |
| CN110756203A (zh) | 一种Ni2P/Mn0.3Cd0.7S光催化分解水复合催化剂及其制备方法与应用 | |
| CN115445594A (zh) | 一种烟气高效协同脱硝脱甲苯的scr催化剂及其制备方法与应用 | |
| CN113578358B (zh) | 一种Pt/NVC-g-C3N4光催化材料及其制备方法和应用 | |
| CN111359676B (zh) | 一种mof基复合材料及其制备方法和应用 | |
| Gao et al. | Tetraphenyl–porphyrin decorated anatase TiO2 catalysts for the visible–light photocatalytic oxidation of gaseous ammonia at room temperature | |
| CN112058291A (zh) | 一种微球状复合可见光催化剂及其快速制备方法和应用 | |
| CN115212909B (zh) | 一种花菜状CdS/C3N4复合材料的水热合成方法及其应用 | |
| CN110813358A (zh) | 一种Ag2O-ZnO/g-C3N4光催化臭氧化催化剂的制备方法 | |
| CN114392759B (zh) | 一种z型光催化剂及其制备方法与应用 | |
| CN113413907B (zh) | 一种复配型近红外光光催化剂及其制备方法和应用 |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231123 Address after: Room 601, Building A, No. 99, Fenghuang 4th Road, Huangpu District (Zhongxin Knowledge City), Guangzhou, Guangdong 510700 (location: Room 642) Patentee after: Maihe (Guangzhou) Industrial Co.,Ltd. Address before: 510000 No. 135 West Xingang Road, Guangzhou, Guangdong, Haizhuqu District Patentee before: SUN YAT-SEN University |