CN113634256B - 一种多维度微纳非贵金属复合催化剂及其制备和应用 - Google Patents
一种多维度微纳非贵金属复合催化剂及其制备和应用 Download PDFInfo
- Publication number
- CN113634256B CN113634256B CN202111088130.1A CN202111088130A CN113634256B CN 113634256 B CN113634256 B CN 113634256B CN 202111088130 A CN202111088130 A CN 202111088130A CN 113634256 B CN113634256 B CN 113634256B
- Authority
- CN
- China
- Prior art keywords
- dimensional
- noble metal
- composite catalyst
- metal composite
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 37
- 239000002905 metal composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 57
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001257 hydrogen Substances 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 42
- 229910000085 borane Inorganic materials 0.000 claims abstract description 30
- 230000007062 hydrolysis Effects 0.000 claims abstract description 30
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 9
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 25
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 229910018864 CoMoO4 Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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
- 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
- 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
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种适用于催化硼烷氨络合物水解制氢的多维度微纳非贵金属复合催化剂及其制备方法和在催化硼烷氨络合物、硼氢化物制氢中的应用。制备方法包括:含有六水合氯化钴、二水合钼酸钠的水溶液于150~180℃水热反应4~8小时,所得CoMo前驱体在氢氩混合气氛下于525~575℃保温1~3小时后冷却至室温。该多维度微纳非贵金属复合催化剂为多相多尺度空间结构自支撑非贵金属复合催化剂,具有零维一维二维特征复合结构,包括二维Co2Mo3O8相正六边形纳米片、零维Co或CoO相纳米颗粒以及上述二维零维两相相互支撑构成的一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒。
Description
技术领域
本发明涉及催化制氢领域,具体涉及一种适用于催化硼烷氨络合物水解制氢的多维度微纳非贵金属复合催化剂及其制备和应用。
背景技术
近年来,由于化石燃料不断加速消耗,环境污染持续加剧,基于可再生能源的替代燃料系统亟待开发。氢能是最理想的绿色燃料之一,其因超高能量密度、高能量转换效率和可再生性而备受关注。然而,如何高效、安全可控地存储和使用氢气仍然是氢经济中的主要问题。
硼烷氨络合物(NH3BH3)具有许多适合化学储氢应用的固有属性,例如非常高的重量储氢密度(19.6wt%)、较低的分子量(30.7g mol-1)、在水中的溶解度大(室温下33.6g/100g)、无毒且在空气中化学性质稳定等。
目前,硼烷氨络合物分解制氢有三种方式:热解制氢、水解制氢和醇解制氢。硼烷氨络合物的热解制氢具有副产物难以调节,最后一当量氢气难以释放的问题,而醇解制氢具有放氢动力学过于缓慢的问题。相较而言,具有适宜放氢温度和放氢动力学的硼烷氨络合物水解制氢最具应用前景。
开发出催化活性优异且经济实惠的催化剂是进一步推进硼烷氨络合物水解制氢应用的关键步骤。目前的研究表明,Pt、Rh、Ru、Ru等贵金属及其合金对于催化硼烷氨络合物水解制氢具有优异的催化活性,但贵金属基催化剂的高成本和低丰度限制了其作为硼烷氨络合物水解制氢催化剂的应用。低成本和高丰度的Fe、Co、Ni、Cu等非贵金属及其衍生物催化剂也表现出良好的催化硼烷氨络合物水解制氢性能。因此,开发出具有高催化活性且制备简单的非贵金属基催化剂应用于硼烷氨络合物水解制氢具有重要意义。
Co及Co氧化物已用于催化硼烷氨络合物水解制氢,然而单独的Co纳米颗粒很容易团聚。利用载体可以在一定程度上分散催化剂,但这会降低单位质量催化剂的效率。通过原位方法制备具有足够分散性的纳米催化剂更难以脱落和团聚。因此,通过原位方法制备具有分散、负载和催化三种作用的多相多尺度自支撑催化剂是实现催化硼烷氨络合物水解制氢高性能的可行解决方案。
水热——热还原法相比于传统的湿化学方法能够更为简单的调控催化剂的结构及相成分。水热步骤可以获得理想空间结构的催化剂前驱体,热还原步骤可以继承前驱体形貌,原位均匀分散地形成金属或金属氧化物催化剂。
发明内容
本发明的目的在于针对现有的硼烷氨络合物水解制氢催化剂成本较高、催化活性偏低等问题,本发明提供了一种适用于催化硼烷氨络合物水解制氢的多维度微纳非贵金属复合催化剂,包括二维正六边形Co2Mo3O8相纳米片和零维Co或CoO相纳米颗粒相互支撑组成的一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒,具有制备工艺简单,材料成本低廉等优势。该催化剂与传统催化硼烷氨络合物、硼氢化物制氢的催化剂相比,可极大降低成本,简化合成方法,易于调控结构成分,并且其催化硼烷氨络合物水解制氢性能得到了极大提升。
一种适用于催化硼烷氨络合物水解制氢的多维度微纳非贵金属复合催化剂,为多相多尺度空间结构自支撑非贵金属复合催化剂,具有零维一维二维特征复合结构,包括二维Co2Mo3O8相正六边形纳米片、零维Co或CoO相纳米颗粒以及上述二维零维两相相互支撑构成的一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒。
一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒中Co2Mo3O8相正六边形纳米片和Co或CoO相纳米颗粒均匀地分散在彼此表面,成分稳定,结构完整,分散均匀,可显著提高催化硼烷氨络合物水解制氢的性能。
作为一个总的发明构思,本发明还提供了所述多维度微纳非贵金属复合催化剂的制备方法,包括步骤:
(1)将六水合氯化钴溶于去离子水中,搅拌分散得到第一物料,将二水合钼酸钠溶于去离子水中,搅拌分散得到第二物料;
(2)在搅拌下,将所述第二物料加入到所述第一物料中,继续搅拌1~3小时,得到第三物料;
(3)将所述第三物料转移到聚四氟乙烯水热反应釜中,升温到150~180℃保温4~8小时,得到CoMo前驱体溶液;
(4)将所述CoMo前驱体溶液从聚四氟乙烯水热反应釜中取出,离心、洗涤、干燥得到CoMo前驱体;
(5)在氢氩混合气的气氛下,将所述CoMo前驱体升温至525~575℃,保温1~3小时后冷却至室温得到适用于催化硼烷氨络合物水解制氢的多相多尺度空间结构自支撑非贵金属复合催化剂。
本发明可以通过水热步骤设计控制CoMo前驱体的空间结构特征,结合热还原温度来调控催化剂的高活性组分及特定空间结构。
本发明通过优选特定催化活性组分,结合原位析出催化活性组分从而有效地抑制团聚现象的产生,提高催化剂的性能与寿命。本发明催化剂中的Co2Mo3O8相为二维正六边形纳米片,Co或CoO相为零维纳米颗粒,这两种高活性组元Co2Mo3O8和Co相或Co2Mo3O8和CoO相具有高的催化活性。特别地,二维Co2Mo3O8相正六边形纳米片和零维Co或CoO相纳米颗粒空间结构互相支撑构成一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒,这种多相多尺度空间结构催化剂相互支撑分散可以提高催化剂整体的结构空间稳定性,能够大幅的提高催化剂的催化活性和循环稳定性,目前无类似结构催化剂应用于硼烷氨络合物水解制氢研究的相关报道。
作为优选,步骤(1)中,六水合氯化钴和二水合钼酸钠的摩尔比为1:1。
在一优选例中,步骤(1)中:
所述第一物料中,六水合氯化钴物质的量与去离子水体积之比为10mmol:87.5mL;
所述第二物料中,二水合钼酸钠物质的量与去离子水体积之比为10mmol:87.5mL。
在一优选例中,步骤(3)中,所述聚四氟乙烯水热反应釜的体积为250mL。
在一优选例中,步骤(3)中,升温到160℃保温6小时。
在一优选例中,步骤(4)中,所述干燥的温度为80℃,时间为8~12小时。
在一优选例中,步骤(5)中,所述氢氩混合气中氢气和氩气的体积比为1:9。
在一优选例中,步骤(5)中,升温速率为5~10℃/min。
在一优选例中,步骤(5)中,升温至525~550℃,保温2小时;
所述多相多尺度空间结构自支撑非贵金属复合催化剂包括二维Co2Mo3O8相正六边形纳米片、零维Co相纳米颗粒以及上述二维零维两相相互支撑构成的一维Co@Co2Mo3O8微米棒。
所述的多维度微纳非贵金属复合催化剂,作为优选,所述二维Co2Mo3O8相正六边形纳米片厚20~50nm,边长为50~200nm;
所述零维Co或CoO相纳米颗粒尺寸为10~50nm;
所述一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒长2~10μm,宽200~500nm。
本发明还提供了所述的多维度微纳非贵金属复合催化剂在催化硼烷氨络合物、硼氢化物制氢中的应用。所述硼氢化物包括本领域中常用的用于制氢的硼氢化物,如硼氢化钠等。
本发明与现有技术相比,主要优点包括:
1)本发明基于协同复合催化思路,通过特定制备方法严格控制氢氩混合气氛下的保温温度优选出对硼烷氨络合物水解制氢具有高活性的Co2Mo3O8与Co相或Co2Mo3O8与CoO相双催化组分。多组分之间具有协同作用,同时复合催化剂中蕴含大量的氧空位,这促进硼烷氨络合物和水分子的吸附和解离,极大提升了Co@Co2Mo3O8和CoO@Co2Mo3O8复合催化剂在硼烷氨络合物水解制氢中的催化活性。
2)相比常规的制备方法,本发明通过水热——热还原法,可获得原位析出的催化剂,实现催化活性成分的超分散和保持特殊的多相多尺度空间结构。多相多尺度空间结构由二维的Co2Mo3O8相正六边形纳米片与零维Co或CoO相纳米颗粒及上述二维零维两相相互支撑堆叠构成一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒组成。一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒中Co2Mo3O8相正六边形纳米片和Co或CoO相纳米颗粒均匀地分散在彼此表面,成分稳定,结构完整,分散均匀,可显著提高催化硼烷氨络合物水解制氢的性能。
3)本发明开发的非贵金属复合催化剂可极大降低原材料成本,制备工艺简单便捷易调控,为开发绿色低成本的非贵金属复合催化剂提供一种有效策略。
附图说明
图1为本发明实施例1制备的CoO@Co2Mo3O8-525非贵金属复合催化剂的扫描电镜照片;
图2为本发明实施例2制备的Co@Co2Mo3O8-550非贵金属复合催化剂的扫描电镜照片;
图3为本发明实施例3制备的Co@Co2Mo3O8-575非贵金属复合催化剂的扫描电镜照片;
图4为本发明实施例2制备的Co@Co2Mo3O8-550非贵金属复合催化剂的透射电镜照片;
图5为本发明实施例1~3与对比例1~4制备的CoMo系列催化剂的XRD图谱;
图6为本发明实施例1~3与对比例1~4制备的CoMo系列催化剂在25℃条件下催化硼烷氨络合物水解制氢性能测试图;
图7为本发明实施例2制备的Co@Co2Mo3O8-550非贵金属复合催化剂在25℃条件下催化硼烷氨络合物水解制氢性能循环性能图。
具体实施方式
下面结合附图及具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法,通常按照常规条件,或按照制造厂商所建议的条件。
实施例1
CoO@Co2Mo3O8-525复合催化剂的制备:
1)称取10mmol六水合氯化钴(CoCl2·6H2O)和二水合钼酸钠(Na2MoO4·2H2O)分别溶于87.5mL去离子水中,在500r/min的磁力搅拌分散30min。将分散好的钼酸钠水溶液转移到氯化钴溶液中,继续在500r/min的磁力搅拌分散1小时,得到CoMo前驱体溶液。将亮红色的CoMo前驱体溶液转移到250mL的聚四氟乙烯反应釜中,160℃水热反应6小时,在室温下冷却,将产物分别去离子水和无水乙醇洗涤后放入烘箱中80℃干燥8小时,得到CoMo前驱体粉末。
2)100mg CoMo前驱体粉末加入到瓷舟中放入管式炉内,在体积分数为10%H2-90%Ar的氢氩混合气氛下以5℃/min的升温速率加热至525℃保温2小时,冷却到室温后得到CoO@Co2Mo3O8-525复合催化剂。
实施例2
Co@Co2Mo3O8-550复合催化剂的制备:
与实施例1的区别仅在于步骤2)中加热至550℃,其余与实施例1均相同,得到Co@Co2Mo3O8-550复合催化剂。
实施例3
Co@Co2Mo3O8-575复合催化剂的制备:
与实施例1的区别仅在于步骤2)中加热至575℃,其余与实施例1均相同,得到Co@Co2Mo3O8-575复合催化剂。
实施例制备的CoO@Co2Mo3O8-525、Co@Co2Mo3O8-550、Co@Co2Mo3O8-575复合催化剂的扫描电镜照片如图1、图2、图3所示。三者宏观相貌上几乎一致,呈现一维棒状长2~10μm,宽200~500nm。所述棒状结构由厚20~50nm、边长为50~200nm的二维正六边形纳米片和10~50nm的零维纳米颗粒构成,大小均匀,结构完整。Co@Co2Mo3O8-575复合催化剂与CoO@Co2Mo3O8-525和Co@Co2Mo3O8-550复合催化剂略微的区别在于二维正六边形纳米片有较为明显的结构坍塌。
实施例2制备的Co@Co2Mo3O8-550复合催化剂的透射电镜照片(TEM)如图4所示,通过TEM看到Co@Co2Mo3O8-550复合催化剂呈现出明显的片状颗粒相互支撑的一维棒状结构。
对比例1
CoMoO4-350催化剂的制备:
与实施例1的区别仅在于步骤2)中加热至350℃,其余与实施例1均相同,得到CoMoO4-350催化剂。
对比例2
CoMoO4@CoMoO4-400复合催化剂的制备:
与实施例1的区别仅在于步骤2)中加热至400℃,其余与实施例1均相同,得到CoMoO4@CoMoO4-400复合催化剂。
对比例3
CoMoO4@CoMoO4-450复合催化剂的制备:
与实施例1的区别仅在于步骤2)中加热至450℃,其余与实施例1均相同,得到CoMoO4@CoMoO4-450复合催化剂。
对比例4
CoO@Co2Mo3O8@CoMoO4-500复合催化剂的制备:
与实施例1的区别仅在于步骤2)中加热至500℃,其余与实施例1均相同,得到CoO@Co2Mo3O8@CoMoO4-500复合催化剂。
CoMo前驱体粉末(precursor)和实施例1~3、对比例1~4所得的CoMo系列催化剂的X射线衍射图谱如图5所示,表明CoMo前驱体为CoMoO4·0.75H2O(PDF-01-074-8729),350℃热还原为CoMoO4(PDF-00-021-0868),400℃热还原为CoMoO4(PDF-00-021-0868),450℃热还原为CoMoO4(PDF-00-021-0868)和CoMoO4(PDF-00-025-1434),500℃热还原为CoMoO4(PDF-00-021-0868)、Co2Mo3O8(PDF-00-034-0511)和CoO(PDF-00-074-2391),525℃热还原为Co2Mo3O8(PDF-00-034-0511)和CoO(PDF-00-074-2391),550℃及575℃热还原为Co2Mo3O8(PDF-00-034-0511)和Co(PDF-00-015-0806)。
应用例
催化剂条件下的硼烷氨络合物水解制氢实验:
为考察CoMo前驱体粉末(precursor)和实施例1~3、对比例1~4所得的CoMo系列催化剂对于硼烷氨络合物水解制氢的催化效果,本发明进行了催化剂条件下的硼烷氨络合物水解制氢实验,实验过程如下:
硼烷氨络合物水解制氢实验在50mL的圆底烧瓶中进行。在室温下,将20mg催化剂与4mL的2mol/L NaOH溶液分别转移到圆底烧瓶中,烧瓶的端口通过橡胶管与装满水的500mL橡胶塞玻璃瓶相连,当氢气产生时,产生的气体会将瓶内等体积的水排除,通过排出水的质量转换为水的体积,即可读出氢气产生的体积。将上述准备好的圆底烧瓶转入25℃的油浴锅中并进行磁力搅拌,搅拌速率为500r/min。将1mmol硼烷氨络合物溶于0.2mL的2mol/L NaOH溶液中,通过注射器将硼烷氨络合物溶液加入到圆底烧瓶中。首次反应结束后重复加入上述硼烷氨络合物溶液四次以测试催化剂的循环性能。
CoMo前驱体粉末(precursor)和实施例1~3、对比例1~4所得的CoMo系列催化剂催化硼烷氨络合物水解制氢的性能如图6所示。实施例2的催化剂具有最佳的催化性能。
本发明实施例2所得的Co@Co2Mo3O8-550催化剂催化硼烷氨络合物水解制氢的循环性能如图7所示,循环稳定性良好。
可见,本发明以Co2Mo3O8与Co相或Co2Mo3O8与CoO相为活性组元,通过原位热还原将析出二维Co2Mo3O8相正六边形纳米片及零维Co或CoO相纳米颗粒组装成自支撑的一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒。所得催化剂具有成分空间结构可调控、催化活性组元分布均匀、催化活性位点多等特征,对硼烷氨络合物水解制氢具有良好的催化活性。在25℃条件下,硼烷氨络合物在Co@Co2Mo3O8催化剂体系中4分钟内完成3个当量的制氢工艺。与传统的贵金属催化剂相比,本发明催化剂具有制备工艺简单、原材料成本低廉、适合工业化生产,是一种很有应用前景的催化剂。
此外应理解,在阅读了本发明的上述描述内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (10)
1.一种适用于催化硼烷氨络合物水解制氢的多维度微纳非贵金属复合催化剂,其特征在于,为多相多尺度空间结构自支撑非贵金属复合催化剂,具有零维一维二维特征复合结构,包括二维Co2Mo3O8相正六边形纳米片、零维Co或CoO相纳米颗粒以及上述二维零维两相相互支撑构成的一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒;
所述多维度微纳非贵金属复合催化剂的制备方法包括步骤:
(1)将六水合氯化钴溶于去离子水中,搅拌分散得到第一物料,将二水合钼酸钠溶于去离子水中,搅拌分散得到第二物料;
(2)在搅拌下,将所述第二物料加入到所述第一物料中,继续搅拌1~3小时,得到第三物料;
(3)将所述第三物料转移到聚四氟乙烯水热反应釜中,升温到150~180℃保温4~8小时,得到CoMo前驱体溶液;
(4)将所述CoMo前驱体溶液从聚四氟乙烯水热反应釜中取出,离心、洗涤、干燥得到CoMo前驱体;
(5)在氢氩混合气的气氛下,将所述CoMo前驱体升温至525~575℃,保温1~3小时后冷却至室温得到适用于催化硼烷氨络合物水解制氢的多相多尺度空间结构自支撑非贵金属复合催化剂。
2.根据权利要求1所述的多维度微纳非贵金属复合催化剂,其特征在于,步骤(1)中,六水合氯化钴和二水合钼酸钠的摩尔比为1:1。
3.根据权利要求1或2所述的多维度微纳非贵金属复合催化剂,其特征在于,步骤(1)中:
所述第一物料中,六水合氯化钴物质的量与去离子水体积之比为10mmol:87.5mL;
所述第二物料中,二水合钼酸钠物质的量与去离子水体积之比为10mmol:87.5mL。
4.根据权利要求1所述的多维度微纳非贵金属复合催化剂,其特征在于,步骤(3)中,升温到160℃保温6小时。
5.根据权利要求1所述的多维度微纳非贵金属复合催化剂,其特征在于,步骤(4)中,所述干燥的温度为80℃,时间为8~12小时。
6.根据权利要求1所述的多维度微纳非贵金属复合催化剂,其特征在于,步骤(5)中,所述氢氩混合气中氢气和氩气的体积比为1:9。
7.根据权利要求1所述的多维度微纳非贵金属复合催化剂,其特征在于,步骤(5)中,升温速率为5~10℃/min。
8.根据权利要求1或7所述的多维度微纳非贵金属复合催化剂,其特征在于,步骤(5)中,升温至525~550℃,保温2小时;
所述多相多尺度空间结构自支撑非贵金属复合催化剂包括二维Co2Mo3O8相正六边形纳米片、零维Co相纳米颗粒以及上述二维零维两相相互支撑构成的一维Co@Co2Mo3O8微米棒。
9.根据权利要求1所述的多维度微纳非贵金属复合催化剂,其特征在于,所述二维Co2Mo3O8相正六边形纳米片厚20~50nm,边长为50~200nm;
所述零维Co或CoO相纳米颗粒尺寸为10~50nm;
所述一维Co@Co2Mo3O8或CoO@Co2Mo3O8微米棒长2~10μm,宽200~500nm。
10.根据权利要求1~9任一权利要求所述的多维度微纳非贵金属复合催化剂在催化硼烷氨络合物、硼氢化物制氢中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111088130.1A CN113634256B (zh) | 2021-09-16 | 2021-09-16 | 一种多维度微纳非贵金属复合催化剂及其制备和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111088130.1A CN113634256B (zh) | 2021-09-16 | 2021-09-16 | 一种多维度微纳非贵金属复合催化剂及其制备和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113634256A CN113634256A (zh) | 2021-11-12 |
CN113634256B true CN113634256B (zh) | 2022-05-03 |
Family
ID=78425935
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111088130.1A Active CN113634256B (zh) | 2021-09-16 | 2021-09-16 | 一种多维度微纳非贵金属复合催化剂及其制备和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113634256B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114361411A (zh) * | 2021-12-14 | 2022-04-15 | 上海应用技术大学 | 一种石墨烯包覆层状双氢氧化物衍生物复合材料及其制备方法和应用 |
CN115555025B (zh) * | 2022-10-31 | 2024-01-26 | 河北建材职业技术学院 | 一种高分散钴钼双金属催化剂的制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106345524A (zh) * | 2016-07-29 | 2017-01-25 | 湖北大学 | 一种用于氨硼烷水解释氢的三元纳米催化剂及其制备方法 |
CN108598399A (zh) * | 2018-04-10 | 2018-09-28 | 陕西科技大学 | 一种氧化钴/氧化钼分级异质结构纳米片及其制备方法 |
CN108940328A (zh) * | 2018-06-28 | 2018-12-07 | 大连理工大学 | 纳米片-纳米棒耦合三维复合材料Ni-Co改性碳化钼电催化制氢催化剂及其制备方法 |
WO2021022988A1 (zh) * | 2019-08-07 | 2021-02-11 | 惠州学院 | 一种Co 3O 4/CuMoO 4复合物及其制备方法和应用 |
CN112553642A (zh) * | 2020-11-27 | 2021-03-26 | 华南理工大学 | 一种基于协同改性的非贵金属析氢电催化剂及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7309479B2 (en) * | 2005-06-29 | 2007-12-18 | Samsung Engineering Co., Ltd. | Cobalt oxide catalysts |
-
2021
- 2021-09-16 CN CN202111088130.1A patent/CN113634256B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106345524A (zh) * | 2016-07-29 | 2017-01-25 | 湖北大学 | 一种用于氨硼烷水解释氢的三元纳米催化剂及其制备方法 |
CN108598399A (zh) * | 2018-04-10 | 2018-09-28 | 陕西科技大学 | 一种氧化钴/氧化钼分级异质结构纳米片及其制备方法 |
CN108940328A (zh) * | 2018-06-28 | 2018-12-07 | 大连理工大学 | 纳米片-纳米棒耦合三维复合材料Ni-Co改性碳化钼电催化制氢催化剂及其制备方法 |
WO2021022988A1 (zh) * | 2019-08-07 | 2021-02-11 | 惠州学院 | 一种Co 3O 4/CuMoO 4复合物及其制备方法和应用 |
CN112553642A (zh) * | 2020-11-27 | 2021-03-26 | 华南理工大学 | 一种基于协同改性的非贵金属析氢电催化剂及其制备方法 |
Non-Patent Citations (1)
Title |
---|
Phase equilibria and thermodynamic properties of ternary oxides in the system Co–Mo–O;K.T. Jacob 等;《Journal of Alloys and Compounds》;19981231;第138-146页 * |
Also Published As
Publication number | Publication date |
---|---|
CN113634256A (zh) | 2021-11-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Xu et al. | Stability and kinetic studies of MOF‐derived carbon‐confined ultrafine Co catalyst for sodium borohydride hydrolysis | |
Luo et al. | Improved hydrogen storage of LiBH 4 and NH 3 BH 3 by catalysts | |
CN113634256B (zh) | 一种多维度微纳非贵金属复合催化剂及其制备和应用 | |
Dou et al. | Shaggy-like Ru-clusters decorated core-shell metal-organic framework-derived CoOx@ NPC as high-efficiency catalyst for NaBH4 hydrolysis | |
Erat et al. | Co/CuO–NiO–Al2O3 catalyst for hydrogen generation from hydrolysis of NaBH4 | |
Zhang et al. | Bimetallic (Zn/Co) MOFs-derived highly dispersed metallic Co/HPC for completely hydrolytic dehydrogenation of ammonia–borane | |
CN113522288B (zh) | 用于催化氨硼烷水解制氢的催化剂及其制备方法和应用 | |
CN111167495B (zh) | 一种氨硼烷制氢用催化剂Ni2-xFex@CN-G及其制备方法 | |
CN107597119B (zh) | 抗积碳型钴基低温甲烷二氧化碳重整催化剂及其制备方法 | |
Zhou et al. | Constructing Ru particles decorated Co3B-CoP heterostructures as a highly active and reusable catalyst for H2 generation by catalyzing NaBH4 hydrolysis | |
CN114345350B (zh) | 一种Co基双金属氧化物催化剂及其制备方法 | |
Wang et al. | Non‐noble metal‐based catalysts applied to hydrogen evolution from hydrolysis of boron hydrides | |
Feng et al. | Copper oxide hollow spheres: synthesis and catalytic application in hydrolytic dehydrogenation of ammonia borane | |
CN108246332B (zh) | 一种二维非贵金属负载型催化剂及其制备方法和应用 | |
Liu et al. | Magnetic CoOx@ C-reduced graphene oxide composite with catalytic activity towards hydrogen generation | |
He et al. | Heterostructured Ni/NiO nanoparticles on 1D porous MoO x for hydrolysis of ammonia borane | |
Farrag | Ultrasmall bimetallic Ru-Co alloy nanoclusters immobilized in amino-functionalized UiO-66 and N-doped carbonaceous zirconium oxide nanocomposite for hydrogen generation | |
CN117443428A (zh) | 一种复合催化剂及其制备方法与应用 | |
Chen et al. | Regulation of Co3O4/Co hetero-structures embedded in N-doped porous carbon as high-efficient catalysts for dehydrogenation of ammonia borane | |
CN113976120A (zh) | 一种高活性CoB催化剂的制备方法 | |
Zhao et al. | Surfactant PVA-Stabilized Co–Mo Nanocatalyst Supported by Graphene Oxide Sheets Toward the Hydrolytic Dehydrogenation of Ammonia Borane | |
CN114471590B (zh) | 乒乓菊状多孔微纳非贵金属间化合物催化剂及其制备和应用 | |
Xu et al. | RuCo@ P Core‐Shell Nanoparticles Filled with Carbon Nanotubes for Highly Effective Catalytic Hydrolysis of Ammonia Borane | |
Ren et al. | Hydrogen production from the hydrolysis of ammonia borane catalyzed by metal catalysts: a review | |
CN115445665B (zh) | 一种用于水合肼分解产氢的复合纳米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 |