CN107442123A - 一种四氧化三钴/碳催化剂的制备方法 - Google Patents
一种四氧化三钴/碳催化剂的制备方法 Download PDFInfo
- Publication number
- CN107442123A CN107442123A CN201710679764.1A CN201710679764A CN107442123A CN 107442123 A CN107442123 A CN 107442123A CN 201710679764 A CN201710679764 A CN 201710679764A CN 107442123 A CN107442123 A CN 107442123A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cotton
- preparation
- cobaltosic oxide
- warming
- 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
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000742 Cotton Polymers 0.000 claims abstract description 35
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 11
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 11
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 11
- 229940033123 tannic acid Drugs 0.000 claims abstract description 11
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 11
- 229920002258 tannic acid Polymers 0.000 claims abstract description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000012298 atmosphere Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000005119 centrifugation Methods 0.000 abstract 1
- 241000219146 Gossypium Species 0.000 description 28
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical class O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 5
- 238000003918 potentiometric titration Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2305/08—Nanoparticles or nanotubes
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种四氧化三钴/碳催化剂的制备方法。所述方法先将洗净的棉布浸渍于单宁酸与硝酸钴的混合溶液中,超声混合均匀后收集棉布,离心,干燥,之后将干燥的棉布在氮气氛围中进行热处理,并进一步于空气氛围热处理即制备得到四氧化三钴/碳催化剂。本发明方法简单、可扩大化制备,制得的催化剂活性纳米粒子小,均匀分散,具有高效的催化性能,且易于回收,能够循环利用。
Description
技术领域
本发明涉及一种高级氧化水处理有机污染物催化剂的制备方法,具体涉及一种四氧化三钴/碳催化剂的制备方法,属于水处理材料制备领域。
背景技术
高级氧化技术(Advanced oxidation processes,AOPs)是近年来迅速发展的一类有效降解有机污染物的处理技术。AOPs具有氧化能力强、反应速率快、适用范围广的特点,通过产生高活性的活性氧组分,直接矿化污染物或氧化污染物提高可生化性,被广泛应用于难降解有机废水、痕量污染物的去除。芬顿(Fenton)反应,作为经典的高级氧化技术之一,能快速产生活性物质羟基自由基降解污染物。但由于Fenton反应需要在酸性条件经行,反应产生的铁泥难以有效处理,使其在水处理应用中严重受限。在近几年的研究中,基于SO4 ·-(硫酸根自由基)发展的新型AOPs备受关注。SO4 ·-主要由过硫酸盐产生,其氧化电位在2.5-3.1V,高于OH·-,具有更强的氧化能力,并且在pH 4-10条件范围内能保持较高的活性。基于硫酸根自由基的高级氧化技术具有较好的应用前景。
催化剂是活化过硫酸盐产生硫酸根自由基最有效的途径。目前,主要的催化剂有钴、铁、锰等过渡金属氧化物及其复合材料。铁、锰基的催化剂的催化活性相对较低,钴基的催化剂,作为目前活性最高的一类催化剂,如四氧化三钴(Co3O4)、四氧化三钴/氧化石墨烯(Co3O4/GO)等被广泛研究。另一方面,通过控制合成超小的活性纳米粒子,增加活性位点的数量,将进一步提高催化剂的催化性能。通常,通过负载Co3O4于高比表面的多孔碳、石墨烯等材料。例如,通过水热的方法,将Co3O4负载于碳纳米管表面(J Am Chem Soc,2012,15849-15857)。通过类似的方法,Co3O4与石墨烯复合的纳米催化剂被报道(The Journal ofPhysical Chemistry C,2016,336-344)。然而,负载方法的复杂性、载体的高成本严重限制了这类方法的扩大化制备及面向实际应用。同时,合成的粉末样催化剂虽然具有高效的催化活性,但其难回收、循环使用操作复杂等缺点降低了粉末催化剂的应用预期。因此,针对这一系列挑战,开发具有易回收、循环使用且具有超小、超分散的活性纳米粒子的高效催化剂对面向硫酸根自由基的实际应用具有重要意义。
棉布,作为纺织业最常用的原料之一,每年有巨大的产量,并产生大量的垃圾。应用这些棉布作为催化剂的原料,在废物利用及经济成本方面都有重要意义。
发明内容
本发明的目的是提供一种简易、高效、可循环使用的四氧化三钴/碳催化剂的制备方法。
实现本发明目的的技术方案如下:
一种四氧化三钴/碳(Co3O4/C)催化剂的制备方法,通过单宁酸与钴粒子络合,再通过氢键作用吸附于棉布中,最后热处理,制得高分散的Co3O4/C催化剂,具体步骤如下:
步骤1,配置单宁酸与硝酸钴的混合溶液,将洗净的棉布浸渍在混合溶液中,超声混合均匀,收集棉布,离心,干燥;
步骤2,将干燥的棉布置于氮气氛围中,升温至500~600℃,保温,碳化得到预处理样品;
步骤3,将预处理样品于空气中以1~3℃/min的速率升温至180~220℃,加热10~20h,单质钴/碳经氧化得到四氧化三钴/碳催化剂。
优选地,步骤1中,所述的单宁酸的浓度为50g/L,硝酸钴的浓度为50g/L,超声时间为10~30min,棉布事先经过水、乙醇洗涤3次。
优选地,步骤2中,升温速率为1~5℃/min,保温时间为2~4h。
与现有技术相比,本发明具有以下优点:
(1)制得的Co3O4/C催化剂具有超小、高分散的活性纳米粒子,活化过硫酸盐的催化活性高,在浓度为10ppm的双酚A,氧化剂(过一硫酸盐,PMS)浓度为100ppm,温度为25℃,催化剂投加量为100mg/L的条件下,催化降解效率在10min内达到99%,并且催化剂易回收,可循环使用;
2)本发明方法简单,原料廉价易得,制备简单,可扩大化制备。
附图说明
图1为Co3O4/C的透射电镜图。
图2为Co3O4/C的扫描电镜图。
图3为催化剂降解示意图。
图4为催化剂循环使用图。
具体实施方式
下面结合实施例和附图对本发明作进一步详述。
实施例1
(1)将20g六水合硝酸钴,20g单宁酸溶于400mL的水中,保持搅拌,10min后,加入20g棉布,超声10min,静置50min。取出棉布,在3000rpm下离心20s,将所得的棉布于105℃的烘箱中烘12h。
(2)取10g(1)中所得棉布以3℃/min于惰性氛围升温至500℃,保持2h,然后自然降温。
(3)将所得的碳布(Co/C)以1℃/min于空气环境中升温至180℃,保持12h,然后自然降温,得到Co3O4/C。
图1为Co3O4/C的透射电镜图,从图中可以看出平均直径为7.5nm的Co3O4负载与碳材料上。
图2为Co3O4/C的透射电镜图,从图中可以看出催化剂依然保持了棉布的形貌,易于回收、循环使用。
实施例2
(1)将20g六水合硝酸钴,20g单宁酸溶于400mL的水中,保持搅拌,10min后,加入20g棉布,超声10min,静置50min。取出棉布,在3000rpm下离心20s,将所得的棉布于105℃的烘箱中烘12h。
(2)取10g(1)中所得棉布以3℃/min于惰性氛围升温至600℃,保持2h,然后自然降温。
(3)将所得的碳布(Co/C)以1℃/min于空气环境中升温至180℃,保持12h,然后自然降温,得到Co3O4/C。
实施例3
(1)将20g六水合硝酸钴,20g单宁酸溶于400mL的水中,保持搅拌,10min后,加入20g棉布,超声10min,静置50min。取出棉布,在3000rpm下离心20s,将所得的棉布于105℃的烘箱中烘12h。
(2)取10g(1)中所得棉布以3℃/min于惰性氛围升温至500℃,保持2h,然后自然降温。
(3)将所得的碳布(Co/C)以3℃/min于空气环境中升温至220℃,保持12h,然后自然降温,得到Co3O4/C。
实施例4
(1)将20g六水合硝酸钴,20g单宁酸溶于400mL的水中,保持搅拌,10min后,加入20g棉布,超声10min,静置50min。取出棉布,在3000rpm下离心20s,将所得的棉布于105℃的烘箱中烘12h。
(2)取10g(1)中所得棉布以3℃/min于惰性氛围升温至600℃,保持2h,然后自然降温。
(3)将所得的碳布(Co/C)以3℃/min于空气环境中升温至220℃,保持12h,然后自然降温,得到Co3O4/C。
实施例5
参考现有文献【Applied Catalysis B:Environmental,2010,529-534】制备Co3O4/AC,并经行对照实验。
向待处理溶液中加入过硫酸盐和pH调节剂,再加入催化剂和氧化剂(PMS)。反应过程中生成的硫酸根自由基氧化目标污染物,反应一段时间后,待处理水得到净化。污染物双酚A(BPA)初始浓度为10ppm,催化剂投加量为0.1g/L,PMS投加量为0.1g/L,初始pH=9,温度为25℃的条件下的降解曲线。结果如图3所示,图中—●—表示Co3O4/C对BPA的降解曲线;图中—◆—表示Co3O4/AC对BPA的降解曲线。Co3O4/C的催化作用下,BPA在10min中内去除率达到99%,而对照样Co3O4/AC的降解速率明显低于Co3O4/C,表明Co3O4/C具有高效的催化活性。
实施例6
将0.2g的Co3O4/C填充于1mL的塑料管作为反应固定床,以连续流反应测试其催化性能。污染物双酚A(BPA)初始浓度为10ppm,PMS投加量为0.1g/L,初始pH=9,温度为25℃,流速为2mL/分钟的条件下,取样后,保持样品继续反应20min测试的降解曲线。结果如图4所示,催化剂可以连续降解1500mL的BPA,并保持去除率在95%以上,说明本发明的催化剂易于回收、循环使用。
对比例1
(1)将20g六水合硝酸钴,20g单宁酸溶于400mL的水中,保持搅拌,10min后,加入20g棉布,超声10min,静置50min。取出棉布,在3000rpm下离心20s,将所得的棉布于105℃的烘箱中烘12h。
(2)取10g(1)中所得棉布以3℃/min于惰性氛围升温至500℃,保持2h,然后自然降温。
(3)将所得的碳布(Co/C)以1℃/min于空气环境中升温250℃,保持12h,然后自然降温,得到Co3O4/C。
对比例中,由于步骤3的反应温度过高,使碳过度氧化,会造成Co3O4粒子的团聚,无法制得具有高催化活性的催化剂。
Claims (3)
1.一种四氧化三钴/碳催化剂的制备方法,其特征在于,具体步骤如下:
步骤1,配置单宁酸与硝酸钴的混合溶液,将洗净的棉布浸渍在混合溶液中,超声混合均匀,收集棉布,离心,干燥;
步骤2,将干燥的棉布置于氮气氛围中,升温至500~600℃,保温,碳化得到预处理样品;
步骤3,将预处理样品于空气中以1~3℃/min的速率升温至180~220℃,加热10~20h,单质钴/碳经氧化得到四氧化三钴/碳催化剂。
2.根据权利要求1所述的制备方法,其特征在于,步骤1中,所述的单宁酸的浓度为50g/L,硝酸钴的浓度为50g/L,超声时间为10~30min,棉布事先经过水、乙醇洗涤3次。
3.根据权利要求1所述的制备方法,其特征在于,步骤2中,升温速率为1~5℃/min,保温时间为2~4h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710679764.1A CN107442123B (zh) | 2017-08-10 | 2017-08-10 | 一种四氧化三钴/碳催化剂的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710679764.1A CN107442123B (zh) | 2017-08-10 | 2017-08-10 | 一种四氧化三钴/碳催化剂的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107442123A true CN107442123A (zh) | 2017-12-08 |
CN107442123B CN107442123B (zh) | 2020-06-26 |
Family
ID=60491469
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710679764.1A Active CN107442123B (zh) | 2017-08-10 | 2017-08-10 | 一种四氧化三钴/碳催化剂的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107442123B (zh) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108906052A (zh) * | 2018-06-29 | 2018-11-30 | 南京理工大学 | 零价铁/碳材料催化剂及其制备方法 |
CN108993491A (zh) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | 用改性碳纳米管制备的活化过硫酸盐催化剂及制备和应用 |
CN108993472A (zh) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | 一种二氧化钛碳纳米管复合载体催化剂及制备和应用 |
CN110215919A (zh) * | 2019-05-28 | 2019-09-10 | 浙江大学 | 一种高分散负载型催化剂及其制备方法和应用 |
CN110482660A (zh) * | 2019-07-26 | 2019-11-22 | 北京工业大学 | 一种应用于电芬顿体系的刻蚀石墨毡电极的制备方法及应用 |
CN111013590A (zh) * | 2019-11-21 | 2020-04-17 | 南京理工大学 | 生物炭负载四氧化三钴催化材料的制备方法 |
CN112010280A (zh) * | 2020-08-18 | 2020-12-01 | 华南农业大学 | 一种纳米金属碳材料的制备方法及其在锂硫电池中的应用 |
CN113976158A (zh) * | 2021-10-21 | 2022-01-28 | 华南理工大学 | 一种负载钴氧化物的自掺氮多孔碳催化剂及其制备方法与应用 |
CN114950435A (zh) * | 2022-06-21 | 2022-08-30 | 阜阳师范大学 | 一种钴氧催化剂的制备方法及其产品和应用 |
CN115739089A (zh) * | 2022-03-28 | 2023-03-07 | 贵州大学 | 一种Co-OBC纳米催化剂的制备及其应用方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104492439A (zh) * | 2014-12-10 | 2015-04-08 | 北京化工大学 | 一种炭载铁掺杂四氧化三钴纳米晶复合催化剂及其制备方法 |
CN105749947B (zh) * | 2014-12-16 | 2018-06-26 | 中国科学院大连化学物理研究所 | 一种非贵金属氧还原催化剂及其制备和应用 |
-
2017
- 2017-08-10 CN CN201710679764.1A patent/CN107442123B/zh active Active
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108906052A (zh) * | 2018-06-29 | 2018-11-30 | 南京理工大学 | 零价铁/碳材料催化剂及其制备方法 |
CN108906052B (zh) * | 2018-06-29 | 2021-06-08 | 南京理工大学 | 零价铁/碳材料催化剂及其制备方法 |
CN108993491B (zh) * | 2018-08-16 | 2021-04-06 | 南京工业大学 | 用改性碳纳米管制备的活化过硫酸盐催化剂及制备和应用 |
CN108993491A (zh) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | 用改性碳纳米管制备的活化过硫酸盐催化剂及制备和应用 |
CN108993472A (zh) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | 一种二氧化钛碳纳米管复合载体催化剂及制备和应用 |
CN108993472B (zh) * | 2018-08-16 | 2021-04-13 | 南京工业大学 | 一种二氧化钛碳纳米管复合载体催化剂及制备和应用 |
CN110215919A (zh) * | 2019-05-28 | 2019-09-10 | 浙江大学 | 一种高分散负载型催化剂及其制备方法和应用 |
CN110482660A (zh) * | 2019-07-26 | 2019-11-22 | 北京工业大学 | 一种应用于电芬顿体系的刻蚀石墨毡电极的制备方法及应用 |
CN111013590A (zh) * | 2019-11-21 | 2020-04-17 | 南京理工大学 | 生物炭负载四氧化三钴催化材料的制备方法 |
CN111013590B (zh) * | 2019-11-21 | 2023-06-09 | 南京理工大学 | 生物炭负载四氧化三钴催化材料的制备方法 |
CN112010280A (zh) * | 2020-08-18 | 2020-12-01 | 华南农业大学 | 一种纳米金属碳材料的制备方法及其在锂硫电池中的应用 |
CN113976158A (zh) * | 2021-10-21 | 2022-01-28 | 华南理工大学 | 一种负载钴氧化物的自掺氮多孔碳催化剂及其制备方法与应用 |
CN115739089A (zh) * | 2022-03-28 | 2023-03-07 | 贵州大学 | 一种Co-OBC纳米催化剂的制备及其应用方法 |
CN114950435A (zh) * | 2022-06-21 | 2022-08-30 | 阜阳师范大学 | 一种钴氧催化剂的制备方法及其产品和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN107442123B (zh) | 2020-06-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107442123A (zh) | 一种四氧化三钴/碳催化剂的制备方法 | |
Gao et al. | Oxidative desulfurization process of model fuel under molecular oxygen by polyoxometalate loaded in hybrid material CNTs@ MOF-199 as catalyst | |
CN103934034B (zh) | 负载型铁基金属有机骨架异相Fenton催化剂的制备方法及其应用 | |
CN112675851B (zh) | 一种Fe-MOFs过氧乙酸催化剂及其制备方法与应用 | |
CN108906052A (zh) | 零价铁/碳材料催化剂及其制备方法 | |
CN101623634A (zh) | 包裹贵金属纳米颗粒的核壳纳米催化剂及其方法 | |
CN106268854A (zh) | 还原性氧化石墨烯负载纳米Fe3O4/Mn3O4复合材料及其制备和应用 | |
CN111627588B (zh) | 一种石墨烯气凝胶在光催化去除铀中的应用 | |
CN108097261A (zh) | 一种高效稳定的铁锰复合氧化物催化剂及其制备方法与应用 | |
CN107754785A (zh) | 一种用于低温催化氧化甲醛的石墨烯‑氧化锰复合催化剂及其制备方法 | |
CN109529814B (zh) | 一种可见光驱动的反蛋白石光催化材料、其制备方法及其对水体有机污染物的降解去除 | |
CN107029786A (zh) | 一种磁性复合光催化剂Ppy@CdS/ZnFe2O4及其制备方法和用途 | |
CN108465463A (zh) | 一种低温核壳结构Ce基催化剂及其制备方法和应用 | |
CN112442706B (zh) | 电催化还原co2的负载型金铂合金电极及其制备方法 | |
CN110947385A (zh) | 一种碳封装缺陷铁纳米催化剂及其制备方法与其催化过一硫酸氢盐降解新兴污染物的应用 | |
CN107335422B (zh) | 一种碳功能化氧化铈的制备方法 | |
Liu et al. | Ferric oxide as a support of carbide slag for effective transesterification of triglycerides in soybean oil | |
CN108607569A (zh) | 提高电催化还原co2过程中co选择性的催化剂的合成方法 | |
CN110180556B (zh) | 一种改性四硫化钒芬顿催化剂及其制备方法和应用 | |
CN107999081A (zh) | 一种碳包覆结构纳米铁基费托合成催化剂及其制备方法和应用 | |
CN110102302A (zh) | 一种羰基硫净化用催化剂及其制备方法和应用 | |
CN111701596B (zh) | 一种在温和条件下合成氨的原子级活性位点催化剂制备方法 | |
Qiao et al. | Facile low-temperature supercritical carbonization method to prepare high-loading nickel single atom catalysts for efficient photodegradation of tetracycline | |
CN105642298A (zh) | 还原性石墨烯负载纳米Ce0/Fe0复合材料及其制备方法和应用 | |
Jiang et al. | Preparation of KF–La 2 O 2 CO 3 solid base catalysts and their excellent catalytic activities for transesterification of tributyrin with methanol |
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 |