CN108620113A - 一种氮掺杂的碳-铈复合纳米片的制备方法 - Google Patents
一种氮掺杂的碳-铈复合纳米片的制备方法 Download PDFInfo
- Publication number
- CN108620113A CN108620113A CN201810468717.7A CN201810468717A CN108620113A CN 108620113 A CN108620113 A CN 108620113A CN 201810468717 A CN201810468717 A CN 201810468717A CN 108620113 A CN108620113 A CN 108620113A
- Authority
- CN
- China
- Prior art keywords
- cerium
- carbon
- doping
- composite nano
- preparation
- 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
- 239000002055 nanoplate Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 21
- 229910052799 carbon Inorganic materials 0.000 title claims description 17
- 229910052684 Cerium Inorganic materials 0.000 title claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 150000000703 Cerium Chemical class 0.000 claims abstract description 25
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- KIJXJCBYANQZLF-UHFFFAOYSA-N [Ce].[C] Chemical compound [Ce].[C] KIJXJCBYANQZLF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012695 Ce precursor Substances 0.000 claims abstract description 16
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- QHNLFTCGOUAGOG-UHFFFAOYSA-N [C].[N].[Ce] Chemical compound [C].[N].[Ce] QHNLFTCGOUAGOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- UVKFSMBPRQBNCH-UHFFFAOYSA-M 4,4-diphenylbutan-2-yl-ethyl-dimethylazanium;bromide Chemical compound [Br-].C=1C=CC=CC=1C(CC(C)[N+](C)(C)CC)C1=CC=CC=C1 UVKFSMBPRQBNCH-UHFFFAOYSA-M 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- VZXFEELLBDNLAL-UHFFFAOYSA-N dodecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCC[NH3+] VZXFEELLBDNLAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 2
- 239000000463 material Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 150000001912 cyanamides Chemical class 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical class OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 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 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- HDXXSUQVQKJEBI-UHFFFAOYSA-N carbonic acid;cerium Chemical compound [Ce].OC(O)=O HDXXSUQVQKJEBI-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002351 wastewater Substances 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
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种氮掺杂的碳‑铈复合纳米片的制备方法,解决了现有技术中普通微米级的二氧化铈颗粒对催化氧化并没有明显的效果的问题。本发明的方法为取铈盐和含氮化合物,加去离子水恒温搅拌后,再加入酸溶液,恒温搅拌,制得铈盐浆料;再于高温下反应得到碱式碳酸铈浆料,冷却,离心、洗涤、干燥,得碱式碳酸铈前驱体;再焙烧,得二氧化铈纳米片;将二氧化铈纳米片与乙醇溶液、去离子水混合后再加入单氰胺和表面活性剂,恒温搅拌,再于高温下反应,冷却后,离心、洗涤、干燥,得氮掺杂的碳‑铈复合纳米片前驱体;再在惰性气体气氛下焙烧,得到氮掺杂的碳‑镁复合纳米片。本发明氮掺杂的碳‑铈复合纳米片质量轻,光催化活性高。
Description
技术领域
本发明属于化学合成技术领域,具体涉及一种氮掺杂的碳-铈复合纳米片的制备方法。
背景技术
随着工业、农业现代化的发展,大量的有毒有害且难降解的有机污染物(如氯酚类、农药等)投放入水环境造成水体污染;同时汽车尾气排放造成气体污染,已经严重威胁人类生存。对于这两类污染物,利用稀土金属纳米材料的催化氧化功能可以使农药废水得到有效降解,并能使汽车尾气中CO和NOх转化成对人体和环境无害的二氧化碳和氮气,具有良好的经济和社会效应。因此,引起了人们的广泛关注。
CeO2作为一种非常重要的稀土氧化物,它在汽车尾气净化、化学机械抛光、燃料电池等领域有广阔的发展前景。但是普通微米级的二氧化铈颗粒对催化氧化并没有明显的效果。纳米级的CeO2材料在结构和性能方面都有很大提高,且由于纳米尺寸效应使其具有一些新的物理和化学性质。纳米尺度上的CeO2微晶却可以产生有利于氧化反应的氧空位。因此,制备出具有相对分散、数量多的活性位点和丰富的氧空位的超薄CeO2纳米片成为了本领域技术人员亟待解决的问题。
发明内容
本发明解决的技术问题是:提供一种氮掺杂的碳-铈复合纳米片的制备方法,解决现有技术中普通微米级的二氧化铈颗粒对催化氧化并没有明显的效果的问题。
本发明还提供了采用该制备方法制得的氮掺杂的碳-铈复合纳米片。
本发明采用的技术方案如下:
本发明所述的一种氮掺杂的碳-铈复合纳米片的制备方法,包括以下步骤:
步骤1.制备铈盐浆料:取铈盐和含氮化合物,加去离子水恒温搅拌均匀后,再加入酸溶液,恒温搅拌,制得铈盐浆料;
步骤2.制备碱式碳酸铈前驱体:将步骤1制得的铈盐浆料于高温条件下反应,得到碱式碳酸铈浆料,冷却后,去除上清液,将余下的浆料离心,所得滤饼洗涤后干燥,得到碱式碳酸铈前驱体;
步骤3.制备氧化铈纳米片:将步骤2制得的碱式碳酸铈前驱体焙烧,得到二氧化铈纳米片;
步骤4.制备氮-碳-铈复合物浆料溶液:将步骤3制得的二氧化铈纳米片与乙醇溶液、去离子水混合后制成二氧化铈浆料液,再加入单氰胺和表面活性剂,恒温搅拌,得到氮-碳-铈复合物浆料溶液;
步骤5.制备氮掺杂的碳-铈复合纳米片前驱体:将步骤4制得的氮-碳-铈复合物浆料溶液于高温条件下反应,冷却后,去除上清液,将余下浆料离心,所得滤饼洗涤后,干燥,得到氮掺杂的碳-铈复合纳米片前驱体;
步骤6.将步骤5制得的碳-铈复合纳米片前驱体在惰性气体气氛下焙烧,得到氮掺杂的碳-镁复合纳米片。
进一步地,所述铈盐为六水硝酸铈或碳酸铈,所述含氮化合物选自六亚甲基四胺或氨水,所述酸溶液选自冰醋酸、盐酸或硫酸中的一种,所述表面活性剂选自十二烷基苯磺酸钠、十二烷基溴化铵、十二烷基硫酸钠、十六烷基三甲基溴化铵中的任意一种。
进一步地,按最终产物氮掺杂的碳-镁复合纳米片为1g计,所述步骤1中各原料的用量为:铈盐1~6g,含氮化合物2~10g,酸溶液1~5mL,去离子水50~80mL;
所述步骤4中各原料的用量为:乙醇溶液20~40mL,去离子水20~40mL,单氰胺4~12mL,表面活性剂0.5~2g。
进一步地,所述步骤1中的恒温搅拌的条件为:温度25~50℃,搅拌速率400~800r/min,搅拌时间2~5h;所述步骤2中,将步骤1制得的铈盐浆料于140~180℃条件下反应10~15h;所述步骤4中的恒温搅拌条件为温度25~50℃,搅拌速率400~800r/min,搅拌时间0.5-1h。
进一步地,所述步骤1中,加入酸溶液调节pH值为4.5~8.5;所述步骤3中的焙烧条件为:焙烧温度400~600℃,焙烧时间1~3.0h。
进一步地,所述步骤5中将步骤4制得的氮-碳-铈复合物浆料溶液于140~180℃条件下反应15~20h。
进一步地,所述步骤6中,所述惰性气体选自N2、Ar或He中的任意一种或几种,所述惰性气体气氛下焙烧的条件为:惰性气体流速为10~30mL/min,焙烧温度为400~700℃,焙烧时间为2~4.0h。
进一步地,所述步骤2中的滤饼分别依次用去离子水和乙醇洗涤三次;所述步骤5中的滤饼分别依次用去离子水和乙醇洗涤三次。
进一步地,所述步骤4中的乙醇溶液的乙醇浓度为30%~80%。
本发明还提供了采用如上所述的制备方法制得的氮掺杂的碳-铈复合纳米片。
与现有技术相比,本发明具有以下有益效果:
本发明方法科学,操作简便,生产成本低。采用本发明方法制备的氮掺杂的碳-铈复合纳米片质量轻,光催化活性高,是一种对有机污染物光催化降解效率高的水体污染处理剂;同时也是催化氧化空气污染物如CO等的高效气体净化剂。
采用本发明方法制得的碳-铈复合纳米片比表面积大、厚度小,因此其反应位点可以与反应物充分接触,且光生载流子更易迁移到表面与反应物进行氧化还原反应,从而具有高效的光催化活性。另外,本发明的碳-铈复合纳米片的厚度为纳米尺度乃至于原子尺度,由于大量的原子暴露在纳米片的表面,极易引起表面的晶格失序,从而形成大量的原子缺陷。这些缺陷可以有效地提高光催化剂的可见光吸收能力和光生载流子的分离效率,从而有效地提高了光催化活性。
本发明通过将氮原子引入活性炭sp2杂化的碳原子中而形成一种新型的碳基材料。氮原子的进入促使其周围的碳原子带有正电荷,由此而言,其导电性能优于活性炭。因此,将二维片状CeO2与氮掺杂活性炭复合后,可以增大比表面积、快速、有效地分离光电子-空穴对,提高光催化效率。
附图说明
附图1为本发明的工艺流程图。
附图2为本发明的N-CeO2/C复合纳米片材料的SEM图。
附图3为本发明的氮掺杂的碳-镁复合纳米片对刚果红的吸附和光催化降解图谱。
具体实施方式
实施例1
本实施例提供了本发明的氮掺杂的碳-镁复合纳米片的制备方法,具体为:
步骤1.制备铈盐浆料:将六水硝酸铈(Ce(NO)3·6H2O):1.3026g和六亚甲基四胺(C6H12N4):2.9469g加至70mL去离子水中,恒温25℃搅拌均匀后,再加入3mL冰醋酸,调节体系pH值为8.5,并在温度25℃、搅拌速度450r/min下恒温搅拌4h,制得铈盐浆料;
步骤2.制备碱式碳酸铈前驱体:将该铈盐浆料溶液装入水热反应釜中在160℃下反应12h得到碱式碳酸铈浆料,待自然冷却后,去除上清液,将余下浆料离心,所得滤饼洗涤后去离子水和乙醇分别洗涤3次;然后干燥得到碱式碳酸铈前驱体;
步骤3.制备氧化铈纳米片:将步骤2制得的碱式碳酸铈前驱体置于马弗炉中,在温度550℃下焙烧2h即可得到二氧化铈纳米片;
步骤4.制备氮-碳-铈复合物浆料溶液:将步骤3制得的二氧化铈纳米片用40mL30%乙醇溶液和40mL去离子水制成2.5g/L的浆料溶液,再加入0.3mL单氰胺和1.5g聚乙烯吡咯烷酮(Mw=58000),并在温度25℃、搅拌速度500r/min条件下恒温搅拌30min形成氮-碳-铈复合物浆料溶液;
步骤5.制备氮掺杂的碳-铈复合纳米片前驱体:将步骤4制得的氮-碳-铈复合物浆料溶液在170℃下反应20h,自然冷却后去除上清液,将余下浆料离心,所得滤饼用水醇各离心洗涤三次后,干燥,得到氮掺杂的碳-铈复合纳米片前驱体;
步骤6.将步骤5制得的碳-铈复合纳米片前驱体置于气氛炉N2流量10mL/min温度500℃下焙烧4h即可得到氮掺杂的碳-镁复合纳米片,记为1-N-CeO2@C。
实施例2
本实施例提供了本发明的氮掺杂的碳-镁复合纳米片的制备方法,具体为:
步骤1.制备铈盐浆料:将六水硝酸铈(Ce(NO)3·6H2O):5.8514g和六亚甲基四胺(C6H12N4):9.5842g加至50mL去离子水中,恒温50℃搅拌均匀后,再加入1mL硫酸,调节体系pH值为4.5,并在温度50℃、搅拌速度400r/min下恒温搅拌2h,制得铈盐浆料;
步骤2.制备碱式碳酸铈前驱体:将该铈盐浆料溶液装入水热反应釜中在180℃下反应10h得到碱式碳酸铈浆料,待自然冷却后,去除上清液,将余下浆料离心,所得滤饼洗涤后去离子水和乙醇分别洗涤3次;然后干燥得到碱式碳酸铈前驱体;
步骤3.制备氧化铈纳米片:将步骤2制得的碱式碳酸铈前驱体置于马弗炉中,在温度400℃下焙烧3h即可得到二氧化铈纳米片;
步骤4.制备氮-碳-铈复合物浆料溶液:将步骤3制得的二氧化铈纳米片用20mL80%乙醇溶液和40mL去离子水制成2.5g/L的浆料溶液,再加入0.6mL单氰胺和1.5g十二烷基硫酸钠,并在温度35℃、搅拌速度400r/min条件下恒温搅拌60min形成氮-碳-铈复合物浆料溶液;
步骤5.制备氮掺杂的碳-铈复合纳米片前驱体:将步骤4制得的氮-碳-铈复合物浆料溶液在140℃下反应20h,自然冷却后去除上清液,将余下浆料离心,所得滤饼用水醇各离心洗涤三次后,干燥,得到氮掺杂的碳-铈复合纳米片前驱体;
步骤6.将步骤5制得的碳-铈复合纳米片前驱体置于气氛炉Ar流量30mL/min温度400℃下焙烧4h即可得到氮掺杂的碳-镁复合纳米片,记为2-N-CeO2@C。
实施例3
本实施例提供了本发明的氮掺杂的碳-镁复合纳米片的制备方法,具体为:
步骤1.制备铈盐浆料:将碳酸铈3.5185g和氨水(1moL/L):5.0568g加至80mL去离子水中,恒温35℃搅拌均匀后,再加入5mL盐酸,调节pH值为6,并在温度35℃、搅拌速度800r/min下恒温搅拌5h,制得铈盐浆料;
步骤2.制备碱式碳酸铈前驱体:将该铈盐浆料溶液装入水热反应釜中在140℃下反应15h得到碱式碳酸铈浆料,待自然冷却后,去除上清液,将余下浆料离心,所得滤饼洗涤后去离子水和乙醇分别洗涤3次;然后干燥得到碱式碳酸铈前驱体;
步骤3.制备氧化铈纳米片:将步骤2制得的碱式碳酸铈前驱体置于马弗炉中,在温度600℃下焙烧1h即可得到二氧化铈纳米片;
步骤4.制备氮-碳-铈复合物浆料溶液:将步骤3制得的二氧化铈纳米片用40mL60%乙醇溶液和20mL去离子水制成2.5g/L的浆料溶液,再加入0.6mL单氰胺和2g十二烷基溴化铵,并在温度50℃、搅拌速度800r/min条件下恒温搅拌30min形成氮-碳-铈复合物浆料溶液;
步骤5.制备氮掺杂的碳-铈复合纳米片前驱体:将步骤4制得的氮-碳-铈复合物浆料溶液在180℃下反应15h,自然冷却后去除上清液,将余下浆料离心,所得滤饼用水醇各离心洗涤三次后,干燥,得到氮掺杂的碳-铈复合纳米片前驱体;
步骤6.将步骤5制得的碳-铈复合纳米片前驱体置于气氛炉He流量20mL/min温度700℃下焙烧2h即可得到氮掺杂的碳-镁复合纳米片,记为3-N-CeO2@C。
实施例4
将1-N-CeO2@C置于电镜下观察,其SEM图如附图2所示。由附图2可以看出,1-N-CeO2@C的比表面积大、厚度小,具有纳米尺度。
实施例5
称取40mg 1-N-CeO2@C,加至40mL浓度为50mg/L的刚果红溶液中,并置于光化学反应仪的暗室搅拌30min达到吸附平衡。在吸附平衡的基础上,在功率为350W的氙灯光照下进行光催化降解反应,每隔一段时间取样5mL并用0.22μm的滤膜进行过滤处理,在80min光降解达到平衡。采用紫外可见分光光度计测定溶液浓度,处理数据如附图3所示。
采用同样的方法对2-N-CeO2@C,3-N-CeO2@C和CeO2进行测定,其数据如附图3所示。
由附图3可知,1-N-CeO2@C、2-N-CeO2@C和3-N-CeO2@C较CeO2具有更好的光催化活性。
上述实施例仅为本发明的优选实施方式之一,不应当用于限制本发明的保护范围,但凡在本发明的主体设计思想和精神上作出的毫无实质意义的改动或润色,其所解决的技术问题仍然与本发明一致的,均应当包含在本发明的保护范围之内。
Claims (10)
1.一种氮掺杂的碳-铈复合纳米片的制备方法,其特征在于,包括以下步骤:
步骤1.制备铈盐浆料:取铈盐和含氮化合物,加去离子水恒温搅拌均匀后,再加入酸溶液,恒温搅拌,制得铈盐浆料;
步骤2.制备碱式碳酸铈前驱体:将步骤1制得的铈盐浆料于高温条件下反应,得到碱式碳酸铈浆料,冷却后,去除上清液,将余下的浆料离心,所得滤饼洗涤后干燥,得到碱式碳酸铈前驱体;
步骤3.制备氧化铈纳米片:将步骤2制得的碱式碳酸铈前驱体焙烧,得到二氧化铈纳米片;
步骤4.制备氮-碳-铈复合物浆料溶液:将步骤3制得的二氧化铈纳米片与乙醇溶液、去离子水混合后制成二氧化铈浆料液,再加入单氰胺和表面活性剂,恒温搅拌,得到氮-碳-铈复合物浆料溶液;
步骤5.制备氮掺杂的碳-铈复合纳米片前驱体:将步骤4制得的氮-碳-铈复合物浆料溶液于高温条件下反应,冷却后,去除上清液,将余下浆料离心,所得滤饼洗涤后,干燥,得到氮掺杂的碳-铈复合纳米片前驱体;
步骤6.将步骤5制得的碳-铈复合纳米片前驱体在惰性气体气氛下焙烧,得到氮掺杂的碳-镁复合纳米片。
2.根据权利要求1所述的制备方法,其特征在于,所述铈盐为六水硝酸铈或碳酸铈,所述含氮化合物选自六亚甲基四胺或氨水,所述酸溶液选自冰醋酸、盐酸或硫酸中的一种,所述表面活性剂选自十二烷基苯磺酸钠、十二烷基溴化铵、十二烷基硫酸钠、十六烷基三甲基溴化铵中的任意一种。
3.根据权利要求1所述的制备方法,其特征在于,按最终产物氮掺杂的碳-镁复合纳米片为1g计,所述步骤1中各原料的用量为:铈盐1~6g,含氮化合物2~10g,酸溶液1~5mL,去离子水50~80mL;
所述步骤4中各原料的用量为:乙醇溶液20~40mL,去离子水20~40mL,单氰胺4~12mL,表面活性剂0.5~2g。
4.根据权利要求3所述的制备方法,其特征在于,所述步骤1中的恒温搅拌的条件为:温度25~50℃,搅拌速率400~800r/min,搅拌时间2~5h;所述步骤2中,将步骤1制得的铈盐浆料于140~180℃条件下反应10~15h;所述步骤4中的恒温搅拌条件为温度25~50℃,搅拌速率400~800r/min,搅拌时间0.5-1h。
5.根据权利要求4所述的制备方法,其特征在于,所述步骤1中,加入酸溶液调节pH值为4.5~8.5;所述步骤3中的焙烧条件为:焙烧温度400~600℃,焙烧时间1~3.0h。
6.根据权利要求5所述的制备方法,其特征在于,所述步骤5中将步骤4制得的氮-碳-铈复合物浆料溶液于140~180℃条件下反应15~20h。
7.根据权利要求6所述的制备方法,其特征在于,所述步骤6中,所述惰性气体选自N2、Ar或He中的任意一种或几种,所述惰性气体气氛下焙烧的条件为:惰性气体流速为10~30mL/min,焙烧温度为400~700℃,焙烧时间为2~4.0h。
8.根据权利要求7所述的制备方法,其特征在于,所述步骤2中的滤饼分别依次用去离子水和乙醇洗涤三次;所述步骤5中的滤饼分别依次用去离子水和乙醇洗涤三次。
9.根据权利要求8所述的制备方法,其特征在于,所述步骤4中的乙醇溶液的乙醇浓度为30%~80%。
10.采用1-9任意一项所述的制备方法制得的氮掺杂的碳-铈复合纳米片。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810468717.7A CN108620113B (zh) | 2018-05-16 | 2018-05-16 | 一种氮掺杂的碳-铈复合纳米片的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810468717.7A CN108620113B (zh) | 2018-05-16 | 2018-05-16 | 一种氮掺杂的碳-铈复合纳米片的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108620113A true CN108620113A (zh) | 2018-10-09 |
CN108620113B CN108620113B (zh) | 2020-08-25 |
Family
ID=63693471
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810468717.7A Expired - Fee Related CN108620113B (zh) | 2018-05-16 | 2018-05-16 | 一种氮掺杂的碳-铈复合纳米片的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108620113B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110433816A (zh) * | 2019-09-05 | 2019-11-12 | 电子科技大学 | 一种负载型钴掺杂的二氧化铈纳米片的制备方法 |
CN111180745A (zh) * | 2019-12-30 | 2020-05-19 | 浙江工业大学 | 一种CeOx/MC纳米片材料的制备方法和应用 |
CN115490257A (zh) * | 2022-08-31 | 2022-12-20 | 贵州大学 | 一种n掺杂亚微米球形y2o3的制备方法 |
CN115520893A (zh) * | 2022-08-31 | 2022-12-27 | 贵州大学 | 一种高N掺量纳米CeO2的制备方法 |
CN115739156A (zh) * | 2022-11-24 | 2023-03-07 | 中汽创智科技有限公司 | 一种催化剂载体及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60118848A (ja) * | 1983-12-01 | 1985-06-26 | Ricoh Co Ltd | 電子写真感光体 |
CN107824212A (zh) * | 2017-10-31 | 2018-03-23 | 青岛大学 | 氮掺杂碳‑氧化铈复合材料及其制备与应用 |
CN108238627A (zh) * | 2018-04-20 | 2018-07-03 | 内江师范学院 | 高比表面积微纳米二氧化铈的制备方法 |
-
2018
- 2018-05-16 CN CN201810468717.7A patent/CN108620113B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60118848A (ja) * | 1983-12-01 | 1985-06-26 | Ricoh Co Ltd | 電子写真感光体 |
CN107824212A (zh) * | 2017-10-31 | 2018-03-23 | 青岛大学 | 氮掺杂碳‑氧化铈复合材料及其制备与应用 |
CN108238627A (zh) * | 2018-04-20 | 2018-07-03 | 内江师范学院 | 高比表面积微纳米二氧化铈的制备方法 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110433816A (zh) * | 2019-09-05 | 2019-11-12 | 电子科技大学 | 一种负载型钴掺杂的二氧化铈纳米片的制备方法 |
CN110433816B (zh) * | 2019-09-05 | 2021-09-03 | 电子科技大学 | 一种负载型钴掺杂的二氧化铈纳米片的制备方法 |
CN111180745A (zh) * | 2019-12-30 | 2020-05-19 | 浙江工业大学 | 一种CeOx/MC纳米片材料的制备方法和应用 |
CN115490257A (zh) * | 2022-08-31 | 2022-12-20 | 贵州大学 | 一种n掺杂亚微米球形y2o3的制备方法 |
CN115520893A (zh) * | 2022-08-31 | 2022-12-27 | 贵州大学 | 一种高N掺量纳米CeO2的制备方法 |
CN115520893B (zh) * | 2022-08-31 | 2023-08-18 | 贵州大学 | 一种高N掺量纳米CeO2的制备方法 |
CN115739156A (zh) * | 2022-11-24 | 2023-03-07 | 中汽创智科技有限公司 | 一种催化剂载体及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN108620113B (zh) | 2020-08-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108620113A (zh) | 一种氮掺杂的碳-铈复合纳米片的制备方法 | |
Rohokale et al. | A novel two-step co-precipitation approach of CuS/NiMn2O4 heterostructured nanocatalyst for enhanced visible light driven photocatalytic activity via efficient photo-induced charge separation properties | |
Zhao et al. | A novel Z-scheme CeO2/g-C3N4 heterojunction photocatalyst for degradation of Bisphenol A and hydrogen evolution and insight of the photocatalysis mechanism | |
CN108160093B (zh) | 磷酸银/氮掺杂碳量子点/钒酸铋z型光催化剂及其制备方法和应用 | |
CN102151577B (zh) | 一种Ag3PO4/Mg-Al LDO可见光复合光催化剂及其制备与应用 | |
CN101811044B (zh) | 铌酸钾纳米管光催化剂及其制备方法和应用 | |
CN109847786A (zh) | 一种Z型光催化剂MgAlLDH/CN-H的制备方法及应用 | |
CN110152711A (zh) | 一种CeO2@MoS2/g-C3N4三元复合光催化剂及其制备方法 | |
WO2022083793A1 (zh) | 三维 / 二维 Ni-Co 双金属氧化物 /g-C3N4 纳米复合材料及其制备方法与应用 | |
CN108786859A (zh) | 一种碳掺杂碘氧铋碘酸氧铋异质结构的制备方法 | |
CN102861567B (zh) | 一种漂浮型BiVO4/漂珠复合光催化剂、其制备方法及应用 | |
CN104056620A (zh) | 一种可见光催化剂及其制备方法与应用 | |
CN108380226A (zh) | 一种超薄卤氧化铋纳米片及其制备和应用 | |
CN110252370A (zh) | 一种二维ZnO/g-C3N4复合光催化剂的制备方法及用途 | |
Wen et al. | Fabrication of a zinc tungstate-based a pn heterojunction photocatalysts towards refractory pollutants degradation under visible light irradiation | |
CN106334554A (zh) | 一种在可见光下具有高效光催化活性的ZnO/Ag复合纳米光催化剂 | |
CN103191725A (zh) | BiVO4/Bi2WO6复合半导体材料及其水热制备方法和其应用 | |
CN101972645A (zh) | 可见光响应型半导体光催化剂钒酸铋的制备方法 | |
CN108311162A (zh) | 一种ZnO/BiOI异质结光催化剂的制备方法及其应用 | |
CN110589886A (zh) | 一种碳酸氧铋的制备方法 | |
CN109289872A (zh) | 一种全光谱响应二氧化碳还原复合光催化剂及其制备方法 | |
CN110180565A (zh) | 一种光催化剂Bi5O7Br的合成方法及其应用 | |
CN109675547A (zh) | 一种中空立方体型锡酸锌光催化剂的制备方法及其应用 | |
CN103785425B (zh) | 一种花状Bi2O(OH)2SO4光催化剂的制备方法及应用 | |
CN103933957B (zh) | 一种高结晶、尺寸可控、高能面暴露的多孔单晶纳米二氧化钛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 | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200825 Termination date: 20210516 |
|
CF01 | Termination of patent right due to non-payment of annual fee |