CN108435177A - A kind of porous carbon coating nano metal cobalt composite catalyst and its preparation and application - Google Patents
A kind of porous carbon coating nano metal cobalt composite catalyst and its preparation and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 17
- 239000010941 cobalt Substances 0.000 title claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 title claims 5
- 238000000576 coating method Methods 0.000 title claims 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 7
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 7
- 239000013110 organic ligand Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 3
- 150000001868 cobalt Chemical class 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
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- B01J35/398—Egg yolk like
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- C01B3/065—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 from a hydride
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Abstract
本发明提供了一种多孔碳包覆纳米金属钴复合催化剂及其制备方法和应用。具体步骤包括：(1)金属钴盐和有机配体对苯二甲酸按比例溶解在N,N‑二甲基甲酰胺中，高温自组装合成Co‑MOF前驱体；(2)制备的Co‑MOF在惰性氛围下高温热解得到多孔碳包覆纳米金属钴催化剂。采用这一方法制备的催化剂，无需外加碳源，金属分散均匀，金属粒子不易团聚。将该催化剂用于硼氢化钠水解制氢反应效果优异，可循环使用多次，催化剂稳定性高。
The invention provides a porous carbon-coated nano-metal cobalt composite catalyst, a preparation method and application thereof. The specific steps include: (1) metal cobalt salt and organic ligand terephthalic acid are dissolved in N,N-dimethylformamide in proportion, and the Co-MOF precursor is synthesized by high-temperature self-assembly; (2) the prepared Co-MOF The MOF is pyrolyzed at high temperature under an inert atmosphere to obtain a porous carbon-coated nano-metal cobalt catalyst. The catalyst prepared by this method does not need an external carbon source, the metal is uniformly dispersed, and the metal particles are not easy to agglomerate. The catalyst has an excellent effect of being used in the hydrogen production reaction by hydrolyzing sodium borohydride, can be recycled for many times, and has high catalyst stability.
Description
技术领域technical field
本发明属于材料和能源催化技术领域，具体涉及一种多孔碳包覆纳米金属钴复合催化剂及其制备和应用。The invention belongs to the technical field of materials and energy catalysis, and in particular relates to a porous carbon-coated nano-metal cobalt composite catalyst and its preparation and application.
背景技术Background technique
储氢与制氢是氢能利用过程中所要解决的关键问题之一。化学氢化物储氢相较于传统储氢方式有其无可比拟的优势，如储氢能量密度高、反应条件温和等，近年来在需要高能量密度供氢等特殊场合受到了极大关注。其中，硼氢化钠(NaBH4)是最具有代表性的储氢化合物。硼氢化钠本身的储氢量(质量分数)为10.6％，其饱和水溶液质量分数可达35％，此时的储氢量为7.4％。Hydrogen storage and hydrogen production are one of the key problems to be solved in the process of hydrogen energy utilization. Compared with traditional hydrogen storage methods, chemical hydride hydrogen storage has its incomparable advantages, such as high hydrogen storage energy density and mild reaction conditions. In recent years, it has received great attention in special occasions such as high energy density hydrogen supply. Among them, sodium borohydride (NaBH 4 ) is the most representative hydrogen storage compound. The hydrogen storage capacity (mass fraction) of sodium borohydride itself is 10.6%, and its saturated aqueous solution mass fraction can reach 35%, and the hydrogen storage capacity at this moment is 7.4%.
在常温下，硼氢化钠自发水解反应速率较低。为使硼氢化钠溶液稳定保存，还需要在其水溶液中加入强碱抑制其自发水解反应。因此，在供氢过程中需要通过加入催化剂的方式来加速和控制反应的进行。基于各种过渡金属的催化剂已被证实对催化硼氢化钠水解反应具有良好的活性。但由于硼氢化钠的还原性较强，这对金属催化剂的化学稳定性提出了更高的要求。现有的金属催化剂多为简单的负载型催化剂，金属纳米颗粒在使用过程中极易发生颗粒的团聚和金属离子的流失，从而降低催化剂的催化性能。At room temperature, the spontaneous hydrolysis reaction rate of sodium borohydride is low. In order to keep the sodium borohydride solution stable, it is also necessary to add a strong base to its aqueous solution to inhibit its spontaneous hydrolysis reaction. Therefore, it is necessary to accelerate and control the reaction by adding a catalyst during the hydrogen supply process. Catalysts based on various transition metals have been demonstrated to have good activity in catalyzing the hydrolysis reaction of sodium borohydride. However, due to the strong reducibility of sodium borohydride, this puts forward higher requirements on the chemical stability of metal catalysts. Most of the existing metal catalysts are simple supported catalysts. Metal nanoparticles are prone to agglomeration of particles and loss of metal ions during use, thereby reducing the catalytic performance of the catalyst.
金属有机骨架材料(MOFs)通过金属离子与有机配体自组装形成,具有拓扑结构多样、比表面积大、孔隙率高、孔道规则、孔道尺寸可调等优点，是沸石和碳纳米管之外的又一类重要新型多孔材料，在催化、储能和分离中都有广泛应用。以MOF为前驱体经高温热解制备纳米金属多孔碳催化剂，既能保留结构规整、金属分散均匀的优点，也能显著提高稳定性，为其在催化领域的广泛应用提供了可行性。迄今为止，将多孔碳包覆纳米金属作为催化剂催化硼氢化钠水解制氢反应尚未见报道。Metal-organic frameworks (MOFs) are formed by the self-assembly of metal ions and organic ligands. They have the advantages of diverse topological structures, large specific surface area, high porosity, regular channels, and adjustable channel sizes. They are zeolites and carbon nanotubes. Another important new class of porous materials with broad applications in catalysis, energy storage, and separations. Using MOF as the precursor to prepare nano-metal porous carbon catalysts by high-temperature pyrolysis can not only retain the advantages of regular structure and uniform metal dispersion, but also significantly improve the stability, which provides feasibility for its wide application in the field of catalysis. So far, the use of porous carbon-coated nano-metals as catalysts to catalyze the hydrolysis of sodium borohydride to produce hydrogen has not been reported.
发明内容Contents of the invention
本发明针对负载型金属催化剂制备过程中晶粒尺寸控制的不足，提供了一种MOF衍生金属催化剂的制备方法，通过高温处理钴基MOF材料制备多孔碳包覆纳米金属钴复合催化剂，结构规整，金属分散均匀，金属粒子不易团聚，为制备高效稳定纳米金属催化剂提供了一条有效途径。Aiming at the lack of grain size control in the preparation process of supported metal catalysts, the present invention provides a method for preparing MOF-derived metal catalysts. A porous carbon-coated nano-metal cobalt composite catalyst is prepared by high-temperature treatment of cobalt-based MOF materials, and the structure is regular. The metal is dispersed evenly, and the metal particles are not easy to agglomerate, which provides an effective way for the preparation of efficient and stable nano-metal catalysts.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
(1)钴基MOF材料的制备：将硝酸钴与对苯二甲酸有机配体按摩尔比为1:1的比例混合并溶解于60mL N,N-二甲基甲酰胺中，超声分散；将分散后的溶液转移至100mL水热反应釜中，在110℃下反应24h；反应结束后降至室温，经过滤和乙醇洗涤得到片状固体，在60℃下干燥获得催化剂前驱体；(1) Preparation of cobalt-based MOF materials: Mix cobalt nitrate and terephthalic acid organic ligands at a molar ratio of 1:1 and dissolve them in 60mL N,N-dimethylformamide, and ultrasonically disperse them; The dispersed solution was transferred to a 100mL hydrothermal reactor, and reacted at 110°C for 24 hours; after the reaction was completed, it was cooled to room temperature, filtered and washed with ethanol to obtain a flake solid, and dried at 60°C to obtain a catalyst precursor;
(2)多孔碳包覆纳米金属钴复合材料的制备：将通过步骤(1)制备得到的前驱体置于管式炉中，在氮气氛围中于600～800℃下热解6h，然后降至室温取出，得到多孔碳包覆纳米金属钴复合催化剂。(2) Preparation of porous carbon-coated nano-metal cobalt composites: the precursor prepared by step (1) was placed in a tube furnace, and pyrolyzed at 600-800 °C for 6 h in a nitrogen atmosphere, and then lowered to Take it out at room temperature to obtain a porous carbon-coated nano-metal cobalt composite catalyst.
与现有技术相比，本发明的优点和积极效果是：Compared with prior art, advantage and positive effect of the present invention are:
与已有硼氢化钠水解制氢碳载金属催化剂相比，本发明利用MOF骨架中丰富的有机配体为碳材料制备提供碳源，无需外加碳源，工艺简单易行；制得的多孔碳包覆纳米金属钴复合催化剂具有适宜的比表面积，可调的孔隙结构；结构规整，金属分散均匀，金属粒子不易团聚，稳定性强。Compared with the existing carbon-supported metal catalysts for hydrogen production by hydrolysis of sodium borohydride, the present invention uses the abundant organic ligands in the MOF framework to provide carbon sources for the preparation of carbon materials, without the need for additional carbon sources, and the process is simple and easy; the prepared porous carbon The coated nano-metal cobalt composite catalyst has a suitable specific surface area and an adjustable pore structure; the structure is regular, the metal is uniformly dispersed, the metal particles are not easy to agglomerate, and the stability is strong.
附图说明Description of drawings
图1为实施例2制得催化剂的XRD谱图；Fig. 1 is the XRD spectrum pattern that embodiment 2 makes catalyst;
图2为实施例2制得催化剂的TEM图；Fig. 2 is the TEM figure that embodiment 2 makes catalyst;
图3为实施例2制得催化剂催化硼氢化钠水解制氢性能；Fig. 3 is that embodiment 2 makes catalyst catalytic sodium borohydride hydrolysis hydrogen production performance;
图4为实施例2制得催化剂的重复使用性能。Fig. 4 is the repeated use performance of the catalyst prepared in Example 2.
具体实施方式Detailed ways
以下结合附图和具体实施例对本发明的技术方案作进一步详细的说明，这些实施例仅仅是对本发明实施方式的描述，并不限于这些实施例。The technical solution of the present invention will be described in further detail below in conjunction with the accompanying drawings and specific examples. These examples are only descriptions of the implementation of the present invention, and are not limited to these examples.
实施例1Example 1
称取2.91g六水硝酸钴(0.01mol)和1.66g对苯二甲酸(0.01mol)混合溶解于60mLN,N-二甲基甲酰胺中，将溶液超声分散10min，将分散后的溶液转移至水热反应釜中，放入烘箱内在110℃下反应24h；反应结束后在烘箱内缓慢降至室温，过滤出的固体产物用乙醇洗涤3次，在60℃下干燥4h获得催化剂前驱体；将催化剂前驱体在氮气氛围中于600℃保温6h，得到多孔碳包覆纳米金属钴复合催化剂。Weigh 2.91g cobalt nitrate hexahydrate (0.01mol) and 1.66g terephthalic acid (0.01mol) and mix and dissolve in 60mL N,N-dimethylformamide, ultrasonically disperse the solution for 10min, and transfer the dispersed solution to In a hydrothermal reaction kettle, put it in an oven and react at 110°C for 24h; after the reaction, slowly lower it to room temperature in the oven, wash the filtered solid product with ethanol three times, and dry it at 60°C for 4h to obtain a catalyst precursor; The catalyst precursor was kept at 600° C. for 6 h in a nitrogen atmosphere to obtain a porous carbon-coated nano-metal cobalt composite catalyst.
实施例2Example 2
使用实施例1的制备条件，不同的是催化剂前驱体在氮气氛围中于700℃保温6h。The preparation conditions of Example 1 were used, except that the catalyst precursor was kept at 700° C. for 6 hours in a nitrogen atmosphere.
制得的Co-MOF前驱体和多孔碳包覆纳米金属钴复合催化剂的XRD谱图如图1所示，多孔碳包覆纳米金属钴复合催化剂的TEM图如图2所示。可以看到Co-MOF经过高温焙烧后得到多孔碳和金属钴的复合材料。The XRD patterns of the prepared Co-MOF precursor and the porous carbon-coated nano-metal cobalt composite catalyst are shown in Figure 1, and the TEM images of the porous carbon-coated nano-metal cobalt composite catalyst are shown in Figure 2. It can be seen that Co-MOF is calcined at high temperature to obtain a composite material of porous carbon and metal cobalt.
实施例3Example 3
使用实施例1的制备条件，不同的是催化剂前驱体在氮气氛围中于800℃保温6h。The preparation conditions of Example 1 were used, except that the catalyst precursor was kept at 800° C. for 6 hours in a nitrogen atmosphere.
实施例4Example 4
将实施例2制得的多孔碳包覆纳米金属钴复合催化剂应用于硼氢化钠水解制氢反应，考察催化剂性能。具体步骤为：取5mL去离子水于反应器中，加入100mg硼氢化钠，分别在20℃、30℃、40℃和50℃下进行水解反应，用排水法测量不同反应时间的氢气体积，结果如图3所示。在30℃反应条件，产氢速率为286.4mL/(min·g催化剂)。The porous carbon-coated nano-metal cobalt composite catalyst prepared in Example 2 was applied to the hydrogen production reaction by hydrolysis of sodium borohydride, and the performance of the catalyst was investigated. The specific steps are: take 5mL of deionized water in the reactor, add 100mg of sodium borohydride, carry out the hydrolysis reaction at 20°C, 30°C, 40°C and 50°C respectively, measure the volume of hydrogen gas at different reaction times by the drainage method, and the results As shown in Figure 3. Under the reaction condition of 30℃, the hydrogen production rate was 286.4mL/(min·g catalyst).
实施例5Example 5
将实施例4中在30℃下反应后的催化剂回收，用乙醇洗涤后在同样反应条件下进行重复试验，结果如图4所示。The catalyst reacted at 30° C. in Example 4 was recovered, washed with ethanol, and repeated tests were carried out under the same reaction conditions. The results are shown in FIG. 4 .
实施例6Example 6
将实施例1制得的催化剂应用于硼氢化钠水解制氢反应，反应温度为30℃，其它反应条件同实施例4，产氢速率为255.1mL/(min·g催化剂)。The catalyst prepared in Example 1 was applied to the hydrogen production reaction by hydrolysis of sodium borohydride, the reaction temperature was 30° C., other reaction conditions were the same as in Example 4, and the hydrogen production rate was 255.1 mL/(min·g catalyst).
实施例7Example 7
将实施例3制得的催化剂应用于硼氢化钠水解制氢反应，反应温度为30℃，其它反应条件同实施例4，产氢速率为293.3mL/(min·g催化剂)。The catalyst prepared in Example 3 was applied to the hydrogen production reaction by hydrolysis of sodium borohydride, the reaction temperature was 30° C., other reaction conditions were the same as in Example 4, and the hydrogen production rate was 293.3 mL/(min·g catalyst).
以上实施例仅用以说明本发明的技术方案，而并非对本发明的范围有任何限制；尽管参照前述实施例对本发明进行了详细的说明，对于本领域的普通技术人员来说，依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit the scope of the present invention; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art can still understand the foregoing The technical solutions described in the embodiments are modified, or some of the technical features are equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions claimed in the present invention.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713326A (en) * | 2019-02-11 | 2019-05-03 | 河南理工大学 | The porous carbon coating eight of Heteroatom doping vulcanizes the application of nine cobalt composite catalysts |
| CN109821538A (en) * | 2019-02-27 | 2019-05-31 | 浙江大学 | Carbon film-coated cobalt catalyst for preparing 1,3-propanediol by hydrogenation of glycidol and preparation method thereof |
| CN110523424A (en) * | 2019-08-15 | 2019-12-03 | 广西师范大学 | A catalyst for hydrogen production based on Ru/NPC-CoxO and its preparation method |
| CN110586191A (en) * | 2019-09-18 | 2019-12-20 | 常州大学 | Oxygen evolution catalyst of CoCu-MOF/SNPC compounded by MOF material |
| CN110655654A (en) * | 2019-09-18 | 2020-01-07 | 常州大学 | Preparation and oxygen evolution properties of a two-dimensional layered cobalt-based metal-organic framework (Co-MOF) electrode material |
| CN110732337A (en) * | 2019-10-15 | 2020-01-31 | 常州大学 | Preparation method of Co-MOF-derived Co/N-CNW composite materials |
| CN111841640A (en) * | 2020-06-30 | 2020-10-30 | 杭州师范大学 | A kind of cobalt-based organic catalyst and its preparation method and its application of transforming CO2 to synthesize benzazepine heterocycle |
| CN113713816A (en) * | 2021-07-20 | 2021-11-30 | 湖南大学 | Preparation and application of copper-cobalt/carbon catalyst derived from metal organic framework material |
| CN115873261A (en) * | 2022-12-02 | 2023-03-31 | 广东省科学院化工研究所 | Metal organic framework material and preparation method and application thereof |
| CN119684952A (en) * | 2025-02-20 | 2025-03-25 | 娄城环保(苏州)有限公司 | A waterproof and anti-fouling tile caulking agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2276563A1 (en) * | 2008-04-15 | 2011-01-26 | Sasol Technology (Proprietary) Limited | Catalysts |
| CN105879895A (en) * | 2016-04-27 | 2016-08-24 | 天津工业大学 | Nitrogen-doped porous carbon nanosheet-supported non-noble metal catalyst and preparation method thereof |
| CN107159214A (en) * | 2017-06-22 | 2017-09-15 | 桂林电子科技大学 | A kind of porous active carbon material load cobalt nanometer particle material and its preparation method and application |
-
2018
- 2018-03-26 CN CN201810250142.1A patent/CN108435177A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2276563A1 (en) * | 2008-04-15 | 2011-01-26 | Sasol Technology (Proprietary) Limited | Catalysts |
| CN105879895A (en) * | 2016-04-27 | 2016-08-24 | 天津工业大学 | Nitrogen-doped porous carbon nanosheet-supported non-noble metal catalyst and preparation method thereof |
| CN107159214A (en) * | 2017-06-22 | 2017-09-15 | 桂林电子科技大学 | A kind of porous active carbon material load cobalt nanometer particle material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| KUN-YI ANDREW LIN: "Efficient hydrogen production from NaBH4 hydrolysis catalyzed by a magnetic cobalt/carbon composite derived from a zeolitic imidazolate framework", 《CHEMICAL ENGINEERING JOURNAL》 * |
| XI WANG: "Chemoselective hydrogenation of functionalized nitroarenes using MOF-derived co-based catalysts", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109821538B (en) * | 2019-02-27 | 2020-11-06 | 浙江大学 | Carbon film-coated cobalt catalyst for preparing 1,3-propanediol by hydrogenation of glycidol and preparation method thereof |
| CN110523424B (en) * | 2019-08-15 | 2021-09-07 | 广西师范大学 | A kind of hydrogen production catalyst based on Ru/NPC-CoxO and preparation method |
| CN110523424A (en) * | 2019-08-15 | 2019-12-03 | 广西师范大学 | A catalyst for hydrogen production based on Ru/NPC-CoxO and its preparation method |
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| CN111841640B (en) * | 2020-06-30 | 2022-12-20 | 杭州师范大学 | Cobalt-based organic catalyst, preparation method thereof and CO conversion method thereof 2 Application of synthesizing benzoazacycle |
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