CN108636438B - 一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用 - Google Patents
一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN108636438B CN108636438B CN201810466700.8A CN201810466700A CN108636438B CN 108636438 B CN108636438 B CN 108636438B CN 201810466700 A CN201810466700 A CN 201810466700A CN 108636438 B CN108636438 B CN 108636438B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- oxygen
- photocatalyst
- doped graphene
- graphene
- 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.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 75
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 12
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 10
- 238000011282 treatment Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 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
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0202—Alcohols or phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用,其中,光催化剂中石墨烯的表面及其晶格内部共同掺杂有氧原子和氮原子,且石墨烯表面具有羧基、羰基和/或羟基等含氧官能团。制备时,先将金属酞菁加入到酸和吡啶的混合溶液中,充分反应后得无金属酞菁;然后将无金属酞菁置于石英管式炉中,经程序升温烧结后得氮掺杂石墨烯;再把氮掺杂石墨烯加入混酸中,先超声条件下反应,然后依次经过稀释、洗涤和干燥处理,得氧氮共掺化石墨烯。本发明所得光催化剂主要用于有机染料废水的处理。本发明中的光催化剂不仅制备方法简单、生产成本低,而且具有良好的光催化活性,可有效解决金属资源浪费以及在后处理时会污染环境的问题。
Description
技术领域
本发明属于光催化技术领域,具体涉及一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用。
背景技术
随着工业的发展,环境问题的恶化,污染治理和环境保护引起人们的广泛关注。由于光催化技术能直接利用太阳光作为光源,设备简单、容易控制、彻底降解有机污染物为CO2和H2O以及无二次污染等优点而成为一种理想的环境治理技术。
目前主流的光催化剂主要是半导体(TiO2、ZnO、ZnO和CdS)或贵金属(Au、Pd和Au-Pd),此类光催化剂具有对太阳能的利用率低下、纳米颗粒团聚严重、抑制光致载流子快等缺点,会造成金属资源的浪费和在后处理方面会污染环境等问题。
石墨烯是一种零带隙材料,使其不能独立应用于光催化方面。文献表明,石墨烯只能作为助催化剂,与金属或金属化合物形成复合材料作为光催化剂应用于光催化产氢或降解领域。通过杂原子掺杂的方法,可以打开石墨烯的能带隙,使石墨烯变成半导体,无需与其他材料复合,可以作为一种独立的光催化剂应用于光催化降解有机染料废水。有鉴于此,特提出本发明以解决上述技术问题。
发明内容
针对上述现有技术,本发明提供一种氧氮共掺杂石墨烯光催化剂,以解决金属资源浪费以及在后处理时会污染环境的问题。
为了达到上述目的,本发明所采用的技术方案是:提供一种氧氮共掺杂石墨烯光催化剂,光催化剂中氮原子掺杂于石墨烯的表面及其晶格内部,氧原子以含氧官能团的形式接枝于石墨烯表面,含氧官能团为羧基、羰基和/或羟基。
本发明中的氧氮共掺杂石墨烯光催化剂采用以下方法制得:
(1)将金属酞菁加入到酸和吡啶的混合溶液中,充分反应后得无金属酞菁;
(2)将步骤(1)中所得无金属酞菁置于石英管式炉中,经程序升温烧结后得氮掺杂石墨烯;
(3)把氮掺杂石墨烯加入混酸中,先超声条件下反应,然后依次经过稀释、洗涤和干燥处理,得氧氮共掺化石墨烯。
制备方法可以做如下进一步改进。
进一步,步骤(1)中金属酞菁为锌酞菁、铁酞菁或铜酞菁,其与混合溶液的料液比为1~3:4~10;所述酸为浓盐酸或浓硝酸,其与吡咯的摩尔比为1:4。
进一步,步骤(1)中反应方式为回流,回流温度为100~150℃,回流时间为10~18h。
进一步,步骤(2)中程序升温烧结的具体方法为:升温速率为5℃/min~10℃/min;分别在320℃、380℃、440℃、500℃、780℃保温1h、1h、2h、2h、6h后自然降温。
进一步,步骤(3)中混酸为浓硫酸和浓硝酸的混合物,其中,浓硫酸与浓硝酸的体积比为2~5:1。
进一步,步骤(3)中超声反应的超声频率为40kHz,温度为25~60℃,超声时间为10~150min。
进一步,步骤(3)中洗涤为用去离子水将样品洗涤至中性;干燥的方式为真空干燥或鼓风干燥,干燥温度为40~60℃,干燥时间为12~48h。
本发明中的氧氮共掺杂石墨烯光催化剂主要用于有机染料废水的处理。以含有亚甲基蓝的废水处理为例,处理的具体方法为:将一定量的氧氮共掺杂石墨烯光催化剂加入到亚甲基蓝的溶液中,暗反应搅拌,待达到吸附-脱附平衡后,置于氙灯光源(λ>420)下光照一定时间,过滤,在可见光分光光度计上测定不同光照时间下的吸光度。最终测得,100mg/L的亚甲基蓝有92%被降解掉,表明本发明中的光催化剂对有机染料废水具有良好的处理效果。
本发明的有益效果是:
1.本发明提供的氧氮共掺杂石墨烯光催化剂无需与其他材料复合,在可见光区可以作为一种独立的光催化剂用于光催化降解有机染料废水。
2.本发明提供的氧氮共掺杂石墨烯光催化剂的制备方法简单,生产成本低,光催化活性好,可进行大规模工业化生产。
3.本发明提供的氧氮共掺杂石墨烯光催化剂的应用,操作简单,无二次污染,可循环使用,可望解决实际中环境问题。
附图说明
图1为氧氮共掺杂石墨烯光催化剂的红外谱图;
图2为氧氮共掺杂石墨烯光催化剂的扫描电镜图;
图3为氧氮共掺杂石墨烯光催化剂的光催化降解有机污染物亚甲基蓝图。
具体实施方式
下面结合附图对本发明的具体实施方式做详细的说明。
实施例一
制备一种氧氮共掺杂石墨烯光催化剂,该光催化剂中石墨烯的表面及其晶格内部共同掺杂有氧原子和氮原子,且石墨烯表面具有含氧官能团,含氧官能团为羧基、羰基和/或羟基。光催化剂的制备方法如下:
(1)取30g锌酞菁,加入300ml吡咯和浓盐酸的混合溶液中(吡咯与盐酸的摩尔比为4:1),120℃回流,12h后用稀盐酸溶液进行抽虑洗涤,再用蒸馏水洗涤产物至中性,取出干燥后研磨可得蓝紫色粉末,即无金属酞菁;
(2)将无金属酞菁置于石英管式炉中,使无金属酞菁分别在320℃、380℃、440℃、500℃、780℃保温1h、1h、2h、2h、6h后自然降温,得到氮掺杂石墨烯;升温时,升温速率为5℃/min;
(3)将2g氮杂化石墨烯加入80ml浓硫酸与浓硝酸的混酸中(V浓硫酸:V浓硝酸=3:1),在50℃条件下以40kHz的频率超声反应150min后,稀释,用去离子水洗涤至pH值为7,放入温度为60℃的真空干燥箱中,干燥12h,得到氧氮共掺化石墨烯。
实施例二
制备一种氧氮共掺杂石墨烯光催化剂,该光催化剂中石墨烯的表面及其晶格内部共同掺杂有氧原子和氮原子,且石墨烯表面具有含氧官能团,含氧官能团为羧基、羰基和/或羟基。光催化剂的制备方法如下:
(1)取30g铁酞菁,加入120ml吡咯和浓盐酸的混合溶液中(吡咯与盐酸的摩尔比为4:1),100℃回流,18h后用稀盐酸溶液进行抽虑洗涤,再用蒸馏水洗涤产物至中性,取出干燥后研磨可得无金属酞菁粉末;
(2)将无金属酞菁置于石英管式炉中,使无金属酞菁分别在320℃、380℃、440℃、500℃、780℃保温1h、1h、2h、2h、6h后自然降温,得到氮掺杂石墨烯;升温时,升温速率为10℃/min;
(3)将2g氮杂化石墨烯加入80ml浓硫酸与浓硝酸的混酸中((V浓硫酸:V浓硝酸=2:1),在25℃条件下以40kHz的频率超声反应100min后,稀释,用去离子水洗涤至pH值为7,放入温度为50℃的真空干燥箱中,干燥24h,得到氧氮共掺化石墨烯。
实施例三
制备一种氧氮共掺杂石墨烯光催化剂,该光催化剂中石墨烯的表面及其晶格内部共同掺杂有氧原子和氮原子,且石墨烯表面具有含氧官能团,含氧官能团为羧基、羰基和/或羟基。光催化剂的制备方法如下:
(1)取30g铜酞菁,加入100ml吡咯和浓硝酸的混合溶液中(吡咯与硝酸的摩尔比为4:1),150℃回流,10h后用稀硝酸溶液进行抽虑洗涤,再用蒸馏水洗涤产物至中性,取出干燥后研磨可得无金属酞菁粉末;
(2)将无金属酞菁置于石英管式炉中,使无金属酞菁分别在320℃、380℃、440℃、500℃、780℃保温1h、1h、2h、2h、6h后自然降温,得到氮掺杂石墨烯;升温时,升温速率为5℃/min;
(3)将2g氮杂化石墨烯加入80ml浓硫酸与浓硝酸的混酸中((V浓硫酸:V浓硝酸=5:1),在60℃条件下以40kHz的频率超声反应10min后,稀释,用去离子水洗涤至pH值为7,放入温度为60℃的鼓风干燥箱中,干燥48h,得到氧氮共掺化石墨烯。
为了验证本采用本发明中的制备方法确实能够得到氧氮共掺杂石墨烯光催化剂,对实施例一最终所得样品进行了红外光谱分析,结果如图1所示。从图中可以看到,氧氮共掺杂石墨烯在以3000cm-1为中心处有一个较宽的吸收峰,为羧酸中-OH伸缩振动特征谱带,1638cm-1是-C=O的振动吸收峰,1384cm-1是-OH的平面弯曲振动峰,1092cm-1是C-O官能团的伸缩振动形成的。通过红外光谱图我们可以看出,羧基被成功的引入到氮杂化石墨烯的表面,说明成功制备了氧氮共掺杂石墨烯。另外,采用扫描电镜对最终样品进行了观察,结果如图2所示。从中可以看出,氧氮共掺杂石墨烯的表面积较小,这可能是由于酸化过程中强酸的作用使石墨烯中部分原子间的化学键发生断裂引起的,可以提供更多的活性位点利于光催化进行。
为了考察所制得的氧氮共掺杂石墨烯光催化剂对有机染料废水的降解效果,以实施例一最终所得光催化剂为例,对不同浓度的亚甲基蓝溶液进行了光降解处理,处理的具体方法为:将50mg光催化剂加入到50ml一定浓度的亚甲基蓝溶液中,暗反应搅拌3h,达到吸附脱附平衡后,置于氙灯光源(λ>420)下光照3h,用0.45μm滤头过滤,在可见光分光光度计上测定不同光照时间下的吸光度。不同浓度的亚甲基蓝溶液降解率如表1所示。对于亚甲基蓝浓度为100mg/L的实验组,在用氙灯光源照射的过程中,每隔半小时检测一次亚甲基蓝的降解率,并以此绘制降解率随时间变化的关系图,结果如图3所示。从中可以看出,随着光照时间的延长,有机染料的降解率逐渐增大,而且在光照3h后,降解率达到最大值,即采用本发明中的光催化剂,最佳处理时间为3h。
表1氧氮共掺杂石墨烯光催化剂对不同浓度亚甲基蓝溶液的降解效果
亚甲基蓝溶液浓度(mg/L) | 光照时间(h) | 降解率(%) |
80 | 3 | 93 |
100 | 3 | 92 |
120 | 3 | 70 |
从表中可以看出,本发明所制备出的氧氮共掺杂石墨烯光催化剂对亚甲基蓝具有良好的降解效果。由于本发明中的光催化剂对所有有机染料废水具有类似的降解作用,因此,虽然在本发明的实施例中只是罗列了光催化剂对含有亚甲基蓝的废水的降解效果,但并不能认为光催化剂只对亚甲基蓝起作用,其对其余的有机染料废水也能起到良好的净化效果。同时,实施例二和实施例三中所得到的氧氮共掺杂石墨烯光催化剂与实施例一种所得到的氧氮共掺杂石墨烯光催化剂效果相同,此处没有再对它们的效果进行描述。
虽然结合附图对本发明的具体实施方式进行了详细地描述,但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内,本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。
Claims (6)
1.一种氧氮共掺杂石墨烯光催化剂,其特征在于:所述光催化剂中氮原子掺杂于石墨烯的表面及其晶格内部,氧原子以含氧官能团的形式接枝于石墨烯表面,所述含氧官能团为羧基、羰基和/或羟基;所述光催化剂经过以下步骤制得:
(1)将金属酞菁加入到酸和吡咯的混合溶液中,充分反应后得无金属酞菁;所述金属酞菁为锌酞菁、铁酞菁或铜酞菁,其与所述混合溶液的料液比为1~3:4~10;所述酸为浓盐酸或浓硝酸,其与吡咯的摩尔比为1:4;
(2)将步骤(1)中所得无金属酞菁置于石英管式炉中,经程序升温烧结后得氮掺杂石墨烯;程序升温烧结的具体方法为:升温速率为5℃/min~10℃/min;分别在320℃、380℃、440℃、500℃、780℃保温1h、1h、2h、2h、6h后自然降温;
(3)把氮掺杂石墨烯加入混酸中,先超声条件下反应,然后依次经过稀释、洗涤和干燥处理,得氧氮共掺化石墨烯。
2.根据权利要求1所述的氧氮共掺杂石墨烯光催化剂,其特征在于:步骤(1)中反应方式为回流,回流温度为100~150℃,回流时间为10~18h。
3.根据权利要求1所述的氧氮共掺杂石墨烯光催化剂,其特征在于:步骤(3)中所述混酸为浓硫酸和浓硝酸的混合物,其中,浓硫酸与浓硝酸的体积比为2~5:1。
4.根据权利要求1所述的氧氮共掺杂石墨烯光催化剂,其特征在于:步骤(3)中超声条件下反应的超声频率为40kHz,温度为25~60℃,超声时间为10~150min。
5.根据权利要求1所述的氧氮共掺杂石墨烯光催化剂,其特征在于:步骤(3)中所述洗涤为用去离子水将样品洗涤至中性;所述干燥的方式为真空干燥或鼓风干燥,干燥温度为40~60℃,干燥时间为12~48h。
6.如权利要求1所述的氧氮共掺杂石墨烯光催化剂在有机染料废水处理中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810466700.8A CN108636438B (zh) | 2018-05-16 | 2018-05-16 | 一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810466700.8A CN108636438B (zh) | 2018-05-16 | 2018-05-16 | 一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108636438A CN108636438A (zh) | 2018-10-12 |
CN108636438B true CN108636438B (zh) | 2021-10-26 |
Family
ID=63756050
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810466700.8A Expired - Fee Related CN108636438B (zh) | 2018-05-16 | 2018-05-16 | 一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108636438B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110652993A (zh) * | 2019-09-30 | 2020-01-07 | 成都理工大学 | 一种钴氮杂石墨烯基催化剂催化氨硼烷产氢性能的研究 |
CN111013623A (zh) * | 2019-12-13 | 2020-04-17 | 西北大学 | 一种氮掺杂石墨烯催化剂及其制备方法 |
CN111439801A (zh) * | 2020-04-17 | 2020-07-24 | 中国地质大学(北京) | 一种利用氮化石墨烯复合纳米纤维膜光热光催化协同处理高盐有机废水的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103664965A (zh) * | 2013-09-10 | 2014-03-26 | 常州大学 | 一种制备酞菁微纳米结构的方法 |
CN103663441A (zh) * | 2013-12-04 | 2014-03-26 | 薛卫东 | 一种固相裂解法制备氮杂石墨烯和纳米金属石墨烯的方法 |
CN103985884A (zh) * | 2014-05-21 | 2014-08-13 | 华中科技大学 | 一种氮掺杂碳纳米材料、其制备方法及应用 |
CN104445160A (zh) * | 2014-11-07 | 2015-03-25 | 孙旭阳 | 一种熔融态无机盐反应床制备石墨烯的方法 |
CN106111179A (zh) * | 2016-06-28 | 2016-11-16 | 福州大学 | 一种小尺寸氮掺杂石墨烯光催化剂及其制备方法和应用 |
CN107416807A (zh) * | 2017-08-28 | 2017-12-01 | 天津大学 | 一种氮氧共掺杂三维纳米多孔石墨烯的制备方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103803539B (zh) * | 2014-02-17 | 2015-09-09 | 上海交通大学 | 一种氮掺杂氧化石墨烯材料及其制备方法 |
CN104229781B (zh) * | 2014-09-09 | 2016-01-27 | 东莞市翔丰华电池材料有限公司 | 一种制备高掺氮量氮掺杂石墨烯的方法 |
KR102415010B1 (ko) * | 2014-12-16 | 2022-07-01 | 스텔라 케미파 가부시키가이샤 | 질소 함유 탄소 재료 및 그 제조 방법 |
-
2018
- 2018-05-16 CN CN201810466700.8A patent/CN108636438B/zh not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103664965A (zh) * | 2013-09-10 | 2014-03-26 | 常州大学 | 一种制备酞菁微纳米结构的方法 |
CN103663441A (zh) * | 2013-12-04 | 2014-03-26 | 薛卫东 | 一种固相裂解法制备氮杂石墨烯和纳米金属石墨烯的方法 |
CN103985884A (zh) * | 2014-05-21 | 2014-08-13 | 华中科技大学 | 一种氮掺杂碳纳米材料、其制备方法及应用 |
CN104445160A (zh) * | 2014-11-07 | 2015-03-25 | 孙旭阳 | 一种熔融态无机盐反应床制备石墨烯的方法 |
CN106111179A (zh) * | 2016-06-28 | 2016-11-16 | 福州大学 | 一种小尺寸氮掺杂石墨烯光催化剂及其制备方法和应用 |
CN107416807A (zh) * | 2017-08-28 | 2017-12-01 | 天津大学 | 一种氮氧共掺杂三维纳米多孔石墨烯的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN108636438A (zh) | 2018-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107824210B (zh) | 一种氮掺杂介孔碳包裹的二氧化钛复合光催化剂及其制备方法和应用 | |
CN108568307B (zh) | 氧掺杂多孔的g-C3N4光催化剂及其制备方法与应用 | |
CN109482203B (zh) | 一种Bi/BiOI纳米片状光催化剂的制备方法 | |
CN113333011B (zh) | 一种复合催化剂及其制备方法和应用 | |
CN108636438B (zh) | 一种氧氮共掺杂石墨烯光催化剂及其制备方法和应用 | |
CN109569684B (zh) | 等离子体改性金属氧化物和g-氮化碳共修饰二氧化钛纳米棒复合光催化剂及其制备和应用 | |
CN111453804B (zh) | 一种铁掺杂类石墨相氮化碳/石墨烯多功能纳米复合材料的制备方法 | |
CN109939643A (zh) | α-Fe2O3掺杂生物炭的制备方法及其应用 | |
CN106944118B (zh) | 银和磷杂化石墨相氮化碳纳米片共同修饰的钒酸铋复合光催化剂及其制备方法和应用 | |
CN111450871A (zh) | 一种Mn掺杂g-C3N4负载多孔ZnCo2O4的光催化材料及其制法 | |
CN111530490A (zh) | 一种Co3O4-TiO2异质结负载碳纳米管光催化降解材料及其制法 | |
CN111672502A (zh) | 利用阳极氧化法制备具有光催化活性镧/锰共掺杂氧化钛纳米管的方法 | |
CN106140241A (zh) | 氧离子表面调控的纳米g‑C3N4有机光催化剂及其制备方法和应用 | |
CN114515590A (zh) | 一种异质光催化材料及其制备和应用 | |
CN109158117B (zh) | 一种全光谱响应双掺杂氟化镧/凹凸棒石上转换复合光催化材料及其制备方法与应用 | |
CN108940349B (zh) | 利用铬酸银/硫掺氮化碳z型光催化剂去除染料污染物的方法 | |
CN112934249B (zh) | 一种磷掺杂石墨氮化碳/四氧化三铁复合材料的制备及应用 | |
CN114632513A (zh) | 单原子Au负载钛酸锶/二氧化钛复合光催化剂的制备方法及其应用 | |
CN109012730B (zh) | 一种可见光响应的硼氮共掺杂光催化剂及其制备方法和应用 | |
CN112642456A (zh) | 一种复合光催化剂的制备方法 | |
CN111558370A (zh) | 一种氧缺陷ZnO纳米片CDs复合光催化剂及其制备方法 | |
CN108940348B (zh) | 铬酸银/硫掺氮化碳z型光催化剂及其制备方法 | |
CN107973367B (zh) | 一种Fe掺杂包裹型TiO2光催化剂降解废水的工艺 | |
CN108404948B (zh) | 一种(BiO)2CO3-BiO2-x复合光催化剂及其制备方法和应用 | |
CN112403467A (zh) | TiO2掺杂Co复合光催化剂及其制备方法和在处理含酚废水中的应用 |
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: 20211026 |
|
CF01 | Termination of patent right due to non-payment of annual fee |