CN107020101A - 一种含氧化锌的纳米碳纤维负载镍基催化材料及其制备方法 - Google Patents
一种含氧化锌的纳米碳纤维负载镍基催化材料及其制备方法 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 42
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 35
- 238000005815 base catalysis Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002121 nanofiber Substances 0.000 claims abstract description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 10
- 239000004917 carbon fiber Substances 0.000 claims abstract description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 48
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000013384 organic framework Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- 239000002184 metal Substances 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- 230000003993 interaction Effects 0.000 abstract description 5
- 239000012621 metal-organic framework Substances 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000002109 single walled nanotube Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- -1 alkenyl arene Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/80—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 zinc, cadmium or mercury
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Abstract
本发明涉及加氢技术领域,具体涉及一种镍基催化剂,更具体的来说,是涉及一种含氧化锌的纳米碳纤维负载镍基催化材料及其制备方法;所述镍基催化材料包括如下重量百分数的原料:以氧化物计,氧化锌15‑80%,氧化镍15‑70%,碳纤维5‑40%;本发明通过静电纺丝技术将双金属有机框架包覆在纳米纤维高聚物中,金属组分含量易于调控。由于金属有机框架材料的拓扑结构,使得碳化后的催化材料中的金属之间有较强的相互作用,制得的含氧化锌的纳米碳纤维负载镍基催化材料分散性好,不易聚集。以纳米碳纤维作为基质所得到的催化材料具有介孔结构,有利于反应物的扩散,从而提高了催化选择性。
Description
技术领域
本发明涉及加氢技术领域,具体涉及一种镍基催化剂,更具体的来说,是涉及一种含氧化锌的纳米碳纤维负载镍基催化材料及其制备方法。
背景技术
镍基催化材料常用于加氢领域,比如二烯烃、炔烃以及烯基芳烃的选择性加氢,烯烃和芳烃的饱和加氢。通过优化催化材料中金属镍的分散性能,可以调控催化材料的加氢活性、选择性和稳定性。目前该材料的常用制备方法包括浸渍法、机械混合法、共沉淀法和胶溶法。采用常用制备方法时,为了优化镍的分散性能,一种方法是通过高温焙烧促使镍与基质间形成尖晶石来避免镍的聚集,但镍在基质中,特别是氧化铝基质中,存在着游离镍、体相镍、高分散镍和尖晶石等几种形态,在进行选择性加氢反应时,存在反应初活性较高的问题,需要在还原后进行钝化处理来获得比较好的稳定性能。另一种方法是加入助剂促进镍与基质间形成较强的相互作用,它能有效避免较高温度处理催化材料从来降低后续的还原温度,但是稳定性能不足。
由金属及有机配体组成的金属有机框架(MOFs)材料由于具有可以调控的拓扑结构,在催化领域被广泛研究。但是由于MOFs材料热及化学稳定性差,并且多为粉晶难于分散,因此限制了其在非均相加氢反应中的应用。但是该材料具有的对金属空间上的设计组装和结构调控的特点,在多金属组分催化材料的设计上具有比较好的应用前景。如专利号ZL 200810200041.X公开了一种单壁碳纳米管金属锌有机框架的制备方法,将单壁碳纳米管和强氧化性酸混合,超声波处理、搅拌反应得到酸化的碳纳米管,将醋酸锌水溶液逐滴加入,搅拌反应后,再加入有机配体溶液搅拌反应,可以得到同时具有单壁碳纳米管完美结构和有机金属框架结构的材料。为了使有机金属框架与单壁碳纳米管之间具有比较牢固的相互作用,该种方法在使用前需要对单壁碳纳米管进行酸化处理,影响了产品的选择性能。
发明内容
本发明要解决的技术问题是克服现有技术的缺陷,提供一种高活性、分散性、稳定性、选择性的含氧化锌的纳米碳纤维负载镍基催化材料,以及它的制备方法。
为解决上述技术问题,本发明提供以下技术方案:
一种含氧化锌的纳米碳纤维负载镍基催化材料,包括如下重量百分数的原料:以氧化物计,氧化锌15-80%,氧化镍15-70%,碳纤维5-40%。
作为进一步的具体方案,以氧化物计,氧化锌含量优先选择20-55%,氧化镍优先选择20-60%,其余还有碳纤维10-30%。
一种含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,以纳米纤维高聚物为基质,通过静电纺丝技术将锌镍双金属有机框架材料包覆在纳米纤维高聚物上,然后进行碳化处理,即得。
通过静电纺丝技术将双金属有机框架包覆在纳米纤维高聚物上,可以在较大的范围内调控金属组分的含量。由于金属有机框架材料本身具备的拓扑结构,使得碳化后的催化材料中的金属之间有较强的相互作用,有利于金属的分散,有效的防止了金属聚集现象的发生。氧化锌掺杂在镍之间,使得镍具有高分散性能,解决了常规制备方法得到的镍基催化剂初活性高,活性金属组分易聚集的问题。以纳米碳纤维作为基质所得到的催化材料具有介孔结构,有利于反应物的扩散,从而提高了催化选择性。
进一步的,所述含氧化锌纳米碳纤维负载的镍基催化材料具有介孔结构,比表面积45-110m2/g,孔径10-60nm。
作为进一步的具体方案,含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,包括如下步骤:
(1)将锌镍双金属有机框架材料超声分散于N-N二甲基甲酰胺中;
(2)将纳米纤维高聚物加入到步骤(1)中的混合液中,搅拌4-24h,得到分散均匀的粘稠液体;
(3)对步骤(2)中的粘稠液体进行静电纺丝,得高聚物丝束;纺丝的液面高度为15-25cm,设备电压为15-25kV,喷液速度为5-15mL/h;
(4)在空气气氛下,以1-10℃/min的速率升温至150-200℃,保温0-2h,再以相同的速率升温至400-600℃,对高聚物丝束焙烧1-5h,得到含氧化锌的纳米碳纤维负载镍基催化材料。
其中,锌镍双金属有机框架材料由如下方法制得,步骤如下:
(a)将锌盐和镍盐溶解于N-N二甲基甲酰胺中,配成含锌镍的溶液;
(b)将对苯二甲酸溶解于N-N二甲基甲酰胺中,配成对苯二甲酸溶液;
(c)在搅拌条件下,将锌镍溶液滴加到对苯二甲酸溶液中,滴加完成后继续搅拌0.5-1h,生成产物;
(d)对生成的产物重复抽滤、洗涤2-5次,真空干燥即得。
步骤(a)中锌镍的摩尔比优先选择1.5-2.5,锌盐可以选自硝酸锌、醋酸锌、碳酸锌中的任意一种;镍盐可以选自硝酸镍、醋酸镍、碱式碳酸镍中的任意一种;纳米纤维高聚物为聚乙烯吡咯烷酮和/或聚丙烯腈。
本发明与现有技术相比具有的有益效果是:
通过静电纺丝技术将双金属有机框架包覆在纳米纤维高聚物中,金属组分含量易于调控。由于金属有机框架材料的拓扑结构,使得碳化后的催化材料中的金属之间有较强的相互作用,制得的含氧化锌的纳米碳纤维负载镍基催化材料分散性好,不易聚集。以纳米碳纤维作为基质所得到的催化材料具有介孔结构,有利于反应物的扩散,从而提高了催化选择性。
附图说明
图1为实施例1制备的含氧化锌的纳米碳纤维负载镍基催化材料的TEM表征图;
图2为对比实施例1制备的对比材料的TEM表征图。
图中:1-粉刷头;2-粉刷手柄;4-电机放置槽;5-电机;6-挡板;61-卡槽;7-收缩装置;71-弹簧;72-夹片;8-拉环;9-按钮;10-蓄电池槽;11-滑轮。
具体实施方式
下为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1:
一种含氧化锌的纳米碳纤维负载镍基催化材料,包括如下重量百分数的原料:以氧化物计,氧化锌48%,氧化镍44%,碳纤维8%。
其制备方法,包括如下步骤:
(1)制备锌镍双金属有机框架材料:
(a)将硝酸锌和硝酸镍以1.8:1的摩尔比溶解于N-N二甲基甲酰胺中,配成含锌镍的溶液;
(b)将对苯二甲酸溶解于N-N二甲基甲酰胺中,配成对苯二甲酸溶液;
(c)在搅拌条件下,将锌镍溶液滴加到对苯二甲酸溶液中,滴加完成后继续搅拌0.5h,生成产物;
(d)对生成的产物重复抽滤、洗涤3次,真空干燥即得。
(2)将锌镍双金属有机框架材料超声分散于N-N二甲基甲酰胺中;
(3)将聚乙烯吡咯烷酮加入到步骤(2)中的混合液中,搅拌16h,得到分散均匀的粘稠液体;
(4)对步骤(3)中的粘稠液体进行静电纺丝,得高聚物丝束;纺丝的液面高度为20cm,设备电压为20kV,喷液速度为12mL/h;
(5)在空气气氛下,以8℃/min的速率升温至200℃,保温1h,再以相同的速率升温至600℃,对高聚物丝束焙烧4h,得到具有介孔结构的含氧化锌的纳米碳纤维负载镍基催化材料,其比表面积为83m2/g,孔径30-40nm。
实施例2:
一种含氧化锌的纳米碳纤维负载镍基催化材料,包括如下重量百分数的原料:以氧化物计,氧化锌38%,氧化镍45%,碳纤维17%。
其制备方法,包括如下步骤:
(1)制备锌镍双金属有机框架材料:
(a)将醋酸锌和醋酸镍以1.5:1的摩尔比溶解于N-N二甲基甲酰胺中,配成含锌镍的溶液;
(b)将对苯二甲酸溶解于N-N二甲基甲酰胺中,配成对苯二甲酸溶液;
(c)在搅拌条件下,将锌镍溶液滴加到对苯二甲酸溶液中,滴加完成后继续搅拌1h,生成产物;
(d)对生成的产物重复抽滤、洗涤5次,真空干燥即得。
(2)将锌镍双金属有机框架材料超声分散于N-N二甲基甲酰胺中;
(3)将聚丙烯腈加入到步骤(2)中的混合液中,搅拌24h,得到分散均匀的粘稠液体;
(4)对步骤(3)中的粘稠液体进行静电纺丝,得高聚物丝束;纺丝的液面高度为15cm,设备电压为15kV,喷液速度为5mL/h;
(5)在空气气氛下,以5℃/min的速率升温至150℃,保温2h,再以相同的速率升温至400℃,对高聚物丝束焙烧3h,得到具有介孔结构的含氧化锌的纳米碳纤维负载镍基催化材料,其比表面积为60-80m2/g,孔径30-50nm。
实施例3:
一种含氧化锌的纳米碳纤维负载镍基催化材料,包括如下重量百分数的原料:以氧化物计,氧化锌28%,氧化镍46%,碳纤维26%。
其制备方法,包括如下步骤:
(1)制备锌镍双金属有机框架材料:
(a)将碳酸锌和碱式碳酸镍以2.5:1的摩尔比溶解于N-N二甲基甲酰胺中,配成含锌镍的溶液;
(b)将对苯二甲酸溶解于N-N二甲基甲酰胺中,配成对苯二甲酸溶液;
(c)在搅拌条件下,将锌镍溶液滴加到对苯二甲酸溶液中,滴加完成后继续搅拌0.5h,生成产物;
(d)对生成的产物重复抽滤、洗涤2次,真空干燥即得。
(2)将锌镍双金属有机框架材料超声分散于N-N二甲基甲酰胺中;
(3)将聚乙烯吡咯烷酮和聚丙烯腈混合物加入到步骤(2)中的混合液中,搅拌8h,得到分散均匀的粘稠液体;
(4)对步骤(3)中的粘稠液体进行静电纺丝,得高聚物丝束;纺丝的液面高度为25cm,设备电压为25kV,喷液速度为15mL/h;
(5)在空气气氛下,以1℃/min的速率升温至400℃,对高聚物丝束焙烧1h,得到具有介孔结构的含氧化锌的纳米碳纤维负载镍基催化材料,其比表面积为45-110m2/g,孔径10-60nm。
实施例4:
一种含氧化锌的纳米碳纤维负载镍基催化材料,包括如下重量百分数的原料,以氧化物计,氧化锌55%,氧化镍20%,碳纤维25%。
其制备方法,包括如下步骤:
(1)制备锌镍双金属有机框架材料:
(a)将硝酸锌和碱式碳酸镍以2:1的摩尔比溶解于N-N二甲基甲酰胺中,配成含锌镍的溶液;
(b)将对苯二甲酸溶解于N-N二甲基甲酰胺中,配成对苯二甲酸溶液;
(c)在搅拌条件下,将锌镍溶液滴加到对苯二甲酸溶液中,滴加完成后继续搅拌1h,生成产物;
(d)对生成的产物重复抽滤、洗涤2-5次,真空干燥即得。
(2)将锌镍双金属有机框架材料超声分散于N-N二甲基甲酰胺中;
(3)将聚乙烯吡咯烷酮加入到步骤(2)中的混合液中,搅拌4h,得到分散均匀的粘稠液体;
(4)对步骤(3)中的粘稠液体进行静电纺丝,得高聚物丝束;纺丝的液面高度为20cm,设备电压为20kV,喷液速度为10mL/h;
(5)在空气气氛下,以5℃/min的速率升温至180℃,保温1h,再以相同的速率升温至500℃,对高聚物丝束焙烧4h,得到具有介孔结构的含氧化锌的纳米碳纤维负载镍基催化材料,其比表面积为45-110m2/g,孔径10-60nm。
对比实施例1:
以专利号ZL 200810200041.X公开的制备方法制得单壁碳纳米管金属锌有机框架,对其产物进行表征,得TEM表征图如图2所示。
对比图1和图2可见,本发明提供的方法具有更好的分散性能。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种含氧化锌的纳米碳纤维负载镍基催化材料,其特征在于,包括如下重量百分数的原料:以氧化物计,氧化锌15-80%,氧化镍15-70%,碳纤维5-40%。
2.根据权利要求1所述的含氧化锌的纳米碳纤维负载镍基催化材料,其特征在于,包括如下重量百分数的原料:以氧化物计,氧化锌20-55%,氧化镍20-60%,碳纤维10-30%。
3.一种根据权利要求1或所述的含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,其特征在于,以纳米纤维高聚物为基质,通过静电纺丝技术将锌镍双金属有机框架材料包覆在纳米纤维高聚物上,然后进行碳化处理,即得。
4.根据权利要求3所述的含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,其特征在于,所述含氧化锌纳米碳纤维负载的镍基催化材料具有介孔结构,比表面积45-110m2/g,孔径10-60nm。
5.根据权利要求3所述的含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,其特征在于,包括如下步骤:
(1)将锌镍双金属有机框架材料超声分散于N-N二甲基甲酰胺中;
(2)将纳米纤维高聚物加入到步骤(1)中的混合液中,搅拌4-24h,得到分散均匀的粘稠液体;
(3)对步骤(2)中的粘稠液体进行静电纺丝,得高聚物丝束;纺丝的液面高度为15-25cm,设备电压为15-25kV,喷液速度为5-15mL/h;
(4)在空气气氛下,以1-10℃/min的速率升温至150-200℃,保温0-2h,再以相同的速率升温至400-600℃,对高聚物丝束焙烧1-5h,得到含氧化锌的纳米碳纤维负载镍基催化材料。
6.根据权利要求3所述的含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,其特征在于,所述锌镍双金属有机框架材料由如下方法制得,步骤如下:
(a)将锌盐和镍盐溶解于N-N二甲基甲酰胺中,配成含锌镍的溶液;
(b)将对苯二甲酸溶解于N-N二甲基甲酰胺中,配成对苯二甲酸溶液;
(c)在搅拌条件下,将锌镍溶液滴加到对苯二甲酸溶液中,滴加完成后继续搅拌0.5-1h,生成产物;
(d)对生成的产物重复抽滤、洗涤2-5次,真空干燥即得。
7.根据权利要求6所述的含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,其特征在于,所述步骤(a)中锌镍的摩尔比为1.5-2.5。
8.根据权利要求6所述的含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,其特征在于,所述步骤(a)中的锌盐选自硝酸锌、醋酸锌、碳酸锌中的任意一种。
9.根据权利要求6所述的含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,其特征在于,所述步骤(a)中的镍盐选自硝酸镍、醋酸镍、碱式碳酸镍中的任意一种。
10.根据权利要求3所述的含氧化锌的纳米碳纤维负载镍基催化材料的制备方法,其特征在于,所述纳米纤维高聚物为聚乙烯吡咯烷酮和/或聚丙烯腈。
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108598445A (zh) * | 2018-06-15 | 2018-09-28 | 陕西科技大学 | 碳包裹镍锌双金属氧化物材料及其制备方法与应用 |
CN109433120A (zh) * | 2018-10-30 | 2019-03-08 | 武汉纺织大学 | 具备污染物吸附、催化及荧光跟踪协同功能的纳米纤维凝胶材料及其制备方法 |
CN109589982A (zh) * | 2018-12-26 | 2019-04-09 | 大连工业大学 | 一种氧化镍基复合半导体纳米纤维的制备方法 |
CN110125428A (zh) * | 2019-04-22 | 2019-08-16 | 安徽理工大学 | MOF衍生的分层蛋黄-壳ZnO-Ni@CNT微球的制备及应用 |
CN110306270A (zh) * | 2019-07-22 | 2019-10-08 | 南通汉卓纺织科技有限公司 | 一种吸湿透气三维复合纱线的制备方法 |
CN114502278A (zh) * | 2021-08-26 | 2022-05-13 | 北京航空航天大学 | 金属原子负载型碳纳米纤维催化剂及其制备方法和应用 |
CN114940621A (zh) * | 2022-05-31 | 2022-08-26 | 烟台大学 | 一种含碳纳米纤维的海绵衍生碳/镍锌复合碳化物材料及制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101455975A (zh) * | 2007-12-14 | 2009-06-17 | 北京化工大学 | 多孔碳纳米纤维负载纳米晶粒催化剂及其制备方法 |
CN101664682A (zh) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | 一种非贵金属负载型选择加氢催化剂及其制备方法和应用 |
DE102010045840A1 (de) * | 2010-09-21 | 2012-03-22 | Tu Darmstadt | Ein Katalysator zur Hydrierung von aromatischen Verbindungen zu Cycloolefinen |
-
2017
- 2017-03-24 CN CN201710181438.8A patent/CN107020101B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101455975A (zh) * | 2007-12-14 | 2009-06-17 | 北京化工大学 | 多孔碳纳米纤维负载纳米晶粒催化剂及其制备方法 |
CN101664682A (zh) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | 一种非贵金属负载型选择加氢催化剂及其制备方法和应用 |
DE102010045840A1 (de) * | 2010-09-21 | 2012-03-22 | Tu Darmstadt | Ein Katalysator zur Hydrierung von aromatischen Verbindungen zu Cycloolefinen |
Non-Patent Citations (1)
Title |
---|
ROYA SEDGHI ET AL.: "Preparation of PAN-based Electrospun Nanofiber Webs Containing Ni-ZnO as High Performance Visible Light Photocatalyst", 《FIBERS AND POLYMERS》 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108598445A (zh) * | 2018-06-15 | 2018-09-28 | 陕西科技大学 | 碳包裹镍锌双金属氧化物材料及其制备方法与应用 |
CN109433120A (zh) * | 2018-10-30 | 2019-03-08 | 武汉纺织大学 | 具备污染物吸附、催化及荧光跟踪协同功能的纳米纤维凝胶材料及其制备方法 |
CN109433120B (zh) * | 2018-10-30 | 2021-02-26 | 武汉纺织大学 | 具备污染物吸附、催化及荧光跟踪协同功能的纳米纤维凝胶材料及其制备方法 |
CN109589982A (zh) * | 2018-12-26 | 2019-04-09 | 大连工业大学 | 一种氧化镍基复合半导体纳米纤维的制备方法 |
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CN114940621B (zh) * | 2022-05-31 | 2023-01-10 | 烟台大学 | 一种含碳纳米纤维的海绵衍生碳/镍锌复合碳化物材料及制备方法 |
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