CN108264093B - 一种钴锰尖晶石微球的制备方法 - Google Patents
一种钴锰尖晶石微球的制备方法 Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 42
- 239000011029 spinel Substances 0.000 title claims abstract description 42
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000004005 microsphere Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 19
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000011565 manganese chloride Substances 0.000 claims abstract description 19
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 18
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 18
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 11
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 11
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 11
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 9
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 9
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 9
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 9
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 9
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 12
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- CHZUADMGGDUUEF-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Co+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Co+2] CHZUADMGGDUUEF-UHFFFAOYSA-N 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
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Abstract
本发明提供了一种钴锰尖晶石微球的制备方法,量取氯化锰和氯化钴溶于去离子水中,量取碳酸氢铵作为pH调整剂,混合搅拌,在100~150℃的温度下水热预处理,待反应产物自然冷却后离心过滤,所得沉淀物依次用去离子水和乙醇洗涤,然后干燥得到碳酸钴和碳酸锰前驱体;将获得的碳酸钴和碳酸锰前驱体在500‑700℃的温度下利用马弗炉煅烧前驱体1~3 h,得到锰酸钴尖晶石微球。将制备的钴锰尖晶石微球用于热催化CO2还原研究,发现可得到人工合成有机物燃料(甲烷)。采用本发明的方法合成的锰钴尖晶石为纯相,形貌为球形,比表面积高,并且高能晶面的暴露明显,降低了热催化CO2还原反应的温度,且生成产物有较高选择性。
Description
技术领域
本发明属于化工领域,涉及一种钴锰尖晶石微球,具体来说是一种钴锰尖晶石微球的 制备方法。
背景技术
碳元素是化学工业的重要原料,大量化工产品的主要成分是碳元素,用二氧化碳替代 石油、天然气和众多高分子材料作为未来的“碳源”,具有重要的经济和社会意义。丰田中 央研究所以水和二氧化碳为原料、利用太阳光合成有用物质,能源转换效率提高到全球最 高的4.6%(2016年)。德国巴斯夫公司将二氧化碳转化为具有广泛应用的碳酸脂类高分子 材料。拜尔公司可将火力发电厂烟道气中的二氧化碳作为生产聚胺脂材料的主要原料。碳 酸酯的生产已有稳定的催化剂市场,但CO2的利用率还远远不够,碳氢燃料的转化还处于 应用基础研究阶段。我国及中美气候变化联合声明都将“碳减排”作为建设目标,鼓励基于 富集CO2向燃料的转化。热催化是目前比较成熟并且效率较高的转化CO2为燃料的技术。 如2010年,苏黎世联邦理工学院的Steinfeld教授研究团队在《Science》发表了基于聚光 太阳能技术的热催化裂解CO2制备CO的工作(Science,2010,330,1797);2016年,Dennis教授研究团队在《PNAS》发表了用太阳能对材料的辐射可以改变CO2还原产物的工作(PNAS,2016,113,2579)。然而催化剂的温度均依赖复杂的外加聚光装置,成本较高,并 且转化反应需要较高的温度(1000度以上),在实际应用时仍存在诸多难题。
发明人也曾利用NiFe2O4尖晶石研究了热催化还原CO2转化反应(RSC Adv.,2016,6, 83814),发现氧空位是影响热催化反应的重要因素,但是该材料的比表面积较低,限制了 与反应气的接触面积,进而影响了催化效率。因此,提高热催化反应效率可从催化剂的结 构、形貌及表面氧缺陷来考虑。一般比表面积和氧缺陷密度越大或暴露高能面,催化裂解 二氧化碳的能力越强。Co3O4具有典型的尖晶石结构,其形貌的调控通常取决于[100]和[111] 晶面的相对生长速率,这两种晶面为二价钴比例较高的晶面。锰的掺杂可使尖晶石具有丰 富的化合价,结构上可能具有丰富的氧缺陷。因此,构筑缺陷态的钴锰尖晶石储氧材料可 有效降低脱氧温度,提高热解二氧化碳能力,是一种绿色的化学转换技术。
发明内容
针对现有技术中的上述技术问题,本发明提供了一种钴锰尖晶石微球的制备方法,所 述的这种钴锰尖晶石微球的制备方法要解决现有技术中热催化反应温度高、晶面选择性暴 露的技术问题。
本发明提供了一种钴锰尖晶石微球的制备方法,包括如下步骤:
1)量取氯化锰和氯化钴溶于去离子水中,量取碳酸氢铵作为pH调整剂,氯化钴和氯 化锰的摩尔比为1:9~9:1,氯化钴和氯化锰的摩尔数之和和碳酸氢铵的摩尔比为1:3,将碳酸氢铵加入氯化锰和氯化钴的水溶液中混合搅拌10-30分钟,在100~150℃的 温度下水热预处理0.5~5h,待反应产物自然冷却后离心过滤,所得沉淀物依次用 去离子水和乙醇洗涤,然后干燥得到碳酸钴和碳酸锰前驱体;
2)将步骤1)获得的碳酸钴和碳酸锰前驱体在500-700℃的温度下利用马弗炉煅烧前 驱体1~3h,得到锰酸钴尖晶石微球。
本发明还提供了通过上述的方法制备的一种钴锰尖晶石微球在CO2催化转化领域的应 用。
进一步的,所述的应用中,催化产物为甲烷。
传统制备钴基尖晶石暴露晶面多具有氧化态的性质。本发明通过水热预处理和高温煅 烧,产品暴露的晶面多为二价钴,具有高还原性,从根本上解决了储氧材料低CO2还原活 性的问题。且合成工艺简单,合成周期短、所需生产设备简单,易于实现工业生产;本发明合成的钴锰尖晶石微球为纯相,纯相有助于控制氧缺陷的含量;本发明合成的钴锰尖晶石微球参与的热催化有效降低了反应温度,且生成产物选择性高,产物中CH4的选择性在99%以上。
将本发明制备的钴锰尖晶石微球用于热催化CO2还原研究,发现可得到人工合成有机 物燃料(甲烷)。
本发明和已有技术相比,其技术进步是显著的。本发明的制备工艺简便、所需设备简 单、环境友好;合成的锰钴尖晶石为纯相,形貌为球形,比表面积高,并且高能晶面的暴露明显,降低了热催化CO2还原反应的温度,且生成产物有较高选择性。本发明的方法提 高了产品催化效率,并拓展纳米材料的适用领域。
附图说明
图1为实施例1合成的钴锰尖晶石微球的扫描电镜图。
图2为实施例1合成的钴锰尖晶石微球的透射电镜图,插图为高分辨图像。
图3为实施例3合成的钴锰尖晶石微球的氮吸附脱附曲线。
图4为合成的钴锰尖晶石微球的XRD图谱(Sab=S钴锰)。
图5为实施例1合成的钴锰尖晶石微球进行CO2催化还原反应的活性测试图。
图6为相同条件下纯Co3O4的CO2催化还原反应的活性测试图。
具体实施方式
下面通过具体实施例对本发明进一步阐述,但并不限制本发明。
本发明中各实施例中所用原料的规格及生产厂家信息如下:
CoCl26H2O、MnCl2 4H2O(分析纯)、碳酸氢铵(分析纯),购自国药集团化学试剂有限公司。
本发明的各实施例中的XRD图的获得采用丹东通达有限公司TD3500型X射线衍射仪,TEM采用日本电子JEOL的JEM-2010,SEM采用飞纳科技有限公司的phenom pro 台式扫描电镜,目标气体产物采用天美科技的GC-7900气相色谱仪检测。
实施例1
(1)量取2.63g的氯化锰和0.35g氯化钴溶于去离子水中,量取3.5g的碳酸氢铵作为 pH调整剂,将二者混合搅拌10分钟,在120℃下进行水热预处理。待反应产物自然冷却后离心过滤,所得沉淀物依次用去离子水和乙醇洗涤,然后干燥得到碳酸钴和碳酸锰前驱体;
(2)在500℃温度下利用马弗炉煅烧前驱体5h,得到锰酸钴尖晶石微球;
图1为实施例1合成的钴锰尖晶石微球的扫描电镜图谱。形貌为球形,图2为TEM图,通过计算d值约为0.45nm,此颗粒所代表的晶相指数对应XRD图谱可得出晶面为(1 11)。
实施例2
(1)量取1.75g的氯化锰和1.4g氯化钴溶于去离子水中,量取3.5g的碳酸氢铵作为pH调整剂,将二者混合搅拌20分钟,在100℃下进行水热预处理。待反应产物自然冷却 后离心过滤,所得沉淀物依次用去离子水和乙醇洗涤,然后干燥得到碳酸钴和碳酸锰前驱 体;
(2)在600℃温度下利用马弗炉煅烧前驱体3h,得到锰酸钴尖晶石微球;图3为实施例2合成的钴锰尖晶石微球的氮吸附脱附曲线,样品S46(m(钴):m(锰)=4:6)的比 表面积为48.17m2/g。
实施例3
(1)量取0.29g的氯化锰和3.16g氯化钴溶于去离子水中,量取3.5g的碳酸氢铵作为 pH调整剂,将二者混合搅拌30分钟,在150℃下进行水热预处理。待反应产物自然冷却后离心过滤,所得沉淀物依次用去离子水和乙醇洗涤,然后干燥得到碳酸钴和碳酸锰前驱体;
(2)在700℃温度下利用马弗炉煅烧前驱体0.5h,得到锰酸钴尖晶石微球;图4为制备的锰钴尖晶石微球的XRD图谱。在18.20°、29.35°、31.25°、36.36°、38.87°、44.78°、59.01°、60.67°和65.18°处出现了明显的衍射峰,最大衍射峰出现在36.36°的位置。可归属于Co3O4(JCPDS file no.180408T)四方晶系结构,分别对应(111)、(202)、(220)、 (311)、(004)、(400)、(511)、(404)、和(440)晶面。
应用实施例1
本发明对实施例1--3合成的钴锰尖晶石微球进行CO2催化转化测试,具体方法为:在 350℃,常压条件下进行CO2催化还原生成CH4。其中测试使用的CO2浓度为99.9%,CO2流速为5~10ml min-1。结果如图5所示。
从图5-图6可知,钴锰尖晶石微球具有明显的转化CO2生成甲烷的能力,最高效率可 达6.8umol/g(2.5h),说明该催化剂有较高的稳定性和活性。所有产品的选择性都很高,产物只有甲烷一种。
结果表明:本发明的制备方法所得的钴锰尖晶石微球,由于提高了比表面积和暴露了 高能面,因而提高材料的催化活性,在同样的条件下,其对CO2的催化还原效率比对应的 纯钴基尖晶石催化剂提高了8.5倍左右(图6)。
综上所述,本发明的一种钴锰尖晶石微球的制备方法,最终得到的产物为纯相,比表 面积较高,目标产物比例较高且具有选择性。提出了控制晶面可有效提高产物催化活性的 方法。
进一步,本发明的一种钴锰尖晶石微球的制备方法,该方法具有制备工艺简便、所需 设备简单,易于实现工业化生产。
以上所述仅是本发明的实施方式的举例,应当指出,对于本技术领域的普通技术人员 来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型 也应视为本发明的保护范围。
Claims (2)
1.一种钴锰尖晶石微球的制备方法,其特征在于包括如下步骤:
1)量取氯化锰和氯化钴溶于去离子水中,量取碳酸氢铵作为pH调整剂,氯化钴和氯化锰的摩尔比为1:9~9:1,氯化钴和氯化锰的摩尔数之和和碳酸氢铵的摩尔比为1:3,将碳酸氢铵加入氯化锰和氯化钴的水溶液中混合搅拌10-30分钟,在100~150℃的温度下水热预处理0.5~5h,待反应产物自然冷却后离心过滤,所得沉淀物依次用去离子水和乙醇洗涤,然后干燥得到碳酸钴和碳酸锰前驱体;
2)将步骤1)获得的碳酸钴和碳酸锰前驱体在500-700 ℃的温度下利用马弗炉煅烧前驱体1~3 h,得到钴锰尖晶石微球。
2.通过权利要求1所述的方法制备的一种钴锰尖晶石微球在CO2催化转化制取甲烷中的应用。
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