CN111905818A - 一种mof基二维超薄电催化剂及其制备方法与应用 - Google Patents
一种mof基二维超薄电催化剂及其制备方法与应用 Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000013110 organic ligand Substances 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 24
- 239000012621 metal-organic framework Substances 0.000 description 12
- 239000002086 nanomaterial Substances 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明公开了一种MOF基二维超薄电催化剂及其制备方法,包括以下步骤:S1.将有机配体苯二甲酸溶于有机溶剂中,加入二价镍盐,搅拌30‑60min;再加入三乙胺,继续搅拌30‑60min;对上述溶液进行超声处理7‑10h,且每隔两小时换一次水;超声完毕后使用无水乙醇清洗沉淀;S2.将步骤S1得到的沉淀分散于无水乙醇中,加入铁盐、钴盐或锰盐,控制溶液中铁盐、钴盐或锰盐的浓度为5‑30mM,再进行超声处理;超声完毕后,使溶液在搅拌的条件下反应6‑10h,无水乙醇洗涤沉淀,即可得到MOF基二维超薄电催化剂。本发明还提供了所述MOF基二维超薄电催化剂在电解水中的应用。本发明的MOF基二维超薄电催化剂,具有良好的催化特性。
Description
技术领域
本发明涉及电催化材料合成技术领域,具体涉及一种基于超薄MOF纳米片的表面原位修饰合成电催化剂,其制备方法及其在电解水中的应用。
背景技术
随着全球环境污染及能源匮乏等问题的逐渐加剧,寻求高效的清洁能源代替现有的化石能源是目前的研究重点。煤炭石油天然气等传统化石能源的大量消耗不仅带来能源储量的急剧减低,还引发了严重的环境污染问题。因此,开发新型氢能源等新型清洁低碳的能源对于缓解环境污染问题、解决目前所面临的的能源危机并实现能源的可持续发展具有非常重大的意义。
目前,利用催化剂电解水制氢被认为是实现上述目标的有效途径之一。理论上电解水是生产氢气的有效策略,然而在工业上的应用很大程度上受限于贵金属催化剂,因此开发一种高效、稳定的非贵金属电催化剂取代现有的贵金属催化剂成为了研究热点,高效的电极催化剂对于实绿色可持续能源转化和储存至关重要。由金属离子与有机配体通过配位络合而成的具有有序拓扑结构的金属有机骨架材料(MOFs)具有周期性的多孔结构、高比表面积,结构可调控以及结构的多样性等特点,作为电催化剂在电催化领域表现出了其独特的优势。然而,MOFs类材料目前所面临的问题如导电性较差,结构易于坍塌等依然有待解决。
发明内容
本发明要解决的技术问题是提供一种MOF基二维超薄电催化剂,该电催化剂具有良好的催化特性。
为了解决上述技术问题,本发明提供了如下的技术方案:
本发明第一方面提供了一种MOF基二维超薄电催化剂的制备方法,包括以下步骤:
S1.将有机配体苯二甲酸溶于有机溶剂中,加入二价镍盐,搅拌30-60min;再加入三乙胺,继续搅拌30-60min;对上述溶液进行超声处理7-10h,且每隔两小时换一次水;超声完毕后使用无水乙醇清洗沉淀;
S2.将步骤S1得到的沉淀分散于无水乙醇中,加入铁盐、钴盐或锰盐,控制溶液中铁盐、钴盐或锰盐的浓度为5-30mM,再进行超声处理;超声完毕后,使溶液在搅拌的条件下反应6-10h,无水乙醇洗涤沉淀,即可得到MOF基二维超薄电催化剂。
进一步地,步骤S1中,所述有机溶剂为N,N-二甲基甲酰胺、乙醇和水的混合溶剂。
进一步地,步骤S1中,所述溶液中苯二甲酸的浓度为0.01-0.03mol/L,镍盐的浓度为0.015-0.025mol/L。
进一步地,步骤S1中,所述二价镍盐为氯化镍、硫酸镍、醋酸镍、醋酸镍或其水合物。
本发明中,三乙胺作为表面活性剂,能够控制合成的Ni-MOFs的形貌,从而得到超薄的Ni-MOFs纳米片。
进一步地,步骤S1中,使用细胞粉碎机进行超声处理,超声功率为50-100W,频率设定范围分别运行1-4s和停止2-5s。采用细胞粉碎机进行超声处理,能够使得沉淀分散的更加均匀。
进一步地,步骤S2中,所述铁盐包括氯化亚铁、硫酸亚铁或其水合物,所述钴盐包括氯化钴或其水合物,所述锰盐包括氯化锰或其水合物。
本发明第二方面提供了由第一方面所述的方法制备的MOF基二维超薄电催化剂。
本发明第三方面提供了第二方面所述的MOF基二维超薄电催化剂在电解水中的应用。
本发明的有益效果:
1.本发明通过原子置换反应,采用铁、钴或锰置换Ni-MOF纳米片中的Ni,从而得到了表面修饰有Fe、Co或Mn元素的MOF基二维超薄纳米材料,该纳米材料不仅具有超薄纳米结构,并且其界面上原子结构被优化,具有良好的电催化性能。
2.本发明的MOFs基纳米材料制备方法简单,原料廉价易得,可以作为商业的电催化材料进行推广使用。
附图说明
图1:Fe@Ni-MOFs的透射电镜图;
图2:Fe@Ni-MOFs与Ni-MOFs和共沉积Fe-Ni-MOFs的XPS对比图;
图3:Fe@Ni-MOFs与Ni-MOFs和共沉积Fe-Ni-MOFs在1mol/L氢氧化钾溶液中的CV曲线对比;
图4:Fe@Ni-MOFs与Ni-MOFs和共沉积Fe-Ni-MOFs在1mol/L氢氧化钾溶液中的LSV曲线对比;
图5:Fe@Ni-MOFs与Ni-MOFs和共沉积Fe-Ni-MOFs在1mol/L氢氧化钾溶液中的Tafel曲线对比。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法,所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1:超薄Ni-MOF纳米片的合成
(1)配置反应溶剂:将32ml N,N-二甲基甲酰胺(DMF)、2ml乙醇和2ml水加入到100ml烧杯中,搅拌至完全混合;
(2)称取0.75mmol苯二甲酸边搅拌边加入到上述溶液中,完成后再搅拌30-60min至溶液澄清,备用;
(3)在上述澄清溶液中加入0.75mmol的NiCl2·6H2O,继续搅拌30-60min;
(4)再在上述溶液中加入0.8ml三乙胺,继续搅拌30-60min;
(5)最后,将上述搅拌完毕的溶液利用细胞粉碎机进行超声处理,超声功率为60W,频率设定为运行2s+停止3s,总超声时间为8h,并且每隔两个小时换一次蒸馏水,处理完毕后,使用无水乙醇将得到的沉淀清洗3-5次,得到超薄Ni-MOF纳米片。
实施例2:Fe@Ni-MOFs纳米材料的制备
(1)将实施例1中得到的沉淀用50ml无水乙醇充分分散,超声30min后备用;
(2)向上述溶液中加入氯化亚铁,使得Fe2+的浓度范围为10mM,超声30min;
(3)将超声完毕后的溶液在磁力搅拌下反应6-10h后,利用无水乙醇洗涤沉淀,即可得到Fe@Ni-MOFs纳米材料。
如图1所示,Fe@Ni-MOFs为纳米片结构,并且厚度均匀。图2的结果显示,Fe成功地置换在纳米片的表面,并且Fe的掺杂量大于共掺杂制备得到的Fe-Ni-MOFs。
对比例1:共沉积Fe-Ni-MOFs纳米材料的制备
(1)配置反应溶剂:将32ml N,N-二甲基甲酰胺(DMF)、2ml乙醇和2ml水加入到100ml烧杯中,搅拌至完全混合;
(2)称取0.75mmol苯二甲酸边搅拌边加入到上述溶液中,完成后再搅拌30-60min至溶液澄清,备用;
(3)在上述澄清溶液中加入0.75mmol的NiCl2·6H2O和0.75mmol的氯化亚铁,继续搅拌30-60min;
(4)再在上述溶液中加入0.8ml三乙胺,继续搅拌30-60min;
(5)最后,将上述搅拌完毕的溶液利用细胞粉碎机进行超声处理,超声功率为60W,频率设定为运行2s+停止3s,总超声时间为8h,并且每隔两个小时换一次蒸馏水,处理完毕后,使用无水乙醇将得到的沉淀清洗3-5次,得到共沉积Fe-Ni-MOFs纳米材料。
实施例3:电催化测试
分别将Fe@Ni-MOFs、Ni-MOFs和Fe-Ni-MOFs使用炭黑和Nafion溶液做成糊状后,滴在玻碳电极上进行电化学测试,电解液为1mol/L氢氧化钾溶液,工作电极的转速为1600rpm。
图3为Fe@Ni-MOFs、Ni-MOFs和共沉积Fe-Ni-MOFs在1mol/L氢氧化钾溶液中的CV曲线对比,从图中可以看出,Fe@Ni-MOFs具有更高的极化电流。
图4为三者在的LSV曲线对比,经过IR矫正,Fe@Ni-MOFs表现出更好的电催化性能,在10mAcm-2的电流密度下,过电势为279mV,明显优于Ni-MOFs和共沉积Fe-Ni-MOFs。
图5为三者在的Tafel曲线对比,从图中可以看出,Ni-MOFs的塔菲尔斜率为90.05,Fe-Ni-MOFs的塔菲尔斜率为56.46,而本发明的Fe@Ni-MOFs的塔菲尔斜率为39.84,这表明本发明的Fe@Ni-MOFs具有更好的电催化性能。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例,本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换,均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。
Claims (8)
1.一种MOF基二维超薄电催化剂的制备方法,其特征在于,包括以下步骤:
S1.将有机配体苯二甲酸溶于有机溶剂中,加入二价镍盐,搅拌30-60min;再加入三乙胺,继续搅拌30-60min;对上述溶液进行超声处理7-10h,且每隔两小时换一次水;超声完毕后使用无水乙醇清洗沉淀;
S2.将步骤S1得到的沉淀分散于无水乙醇中,加入铁盐、钴盐或锰盐,控制溶液中铁盐、钴盐或锰盐的浓度为5-30mM,再进行超声处理;超声完毕后,使溶液在搅拌的条件下反应6-10h,无水乙醇洗涤沉淀,即可得到MOF基二维超薄电催化剂。
2.根据权利要求1所述的一种MOF基二维超薄电催化剂的制备方法,其特征在于,步骤S1中,所述有机溶剂为N,N-二甲基甲酰胺、乙醇和水的混合溶剂。
3.根据权利要求1所述的一种MOF基二维超薄电催化剂的制备方法,其特征在于,步骤S1中,所述溶液中苯二甲酸的浓度为0.01-0.03mol/L,镍盐的浓度为0.015-0.025mol/L。
4.根据权利要求1所述的一种MOF基二维超薄电催化剂的制备方法,其特征在于,步骤S1中,所述二价镍盐为氯化镍、硫酸镍、醋酸镍、醋酸镍或其水合物。
5.根据权利要求1所述的一种MOF基二维超薄电催化剂的制备方法,其特征在于,步骤S1中,使用细胞粉碎机进行超声处理,超声功率为50-100W,频率设定范围分别运行1-4s和停止2-5s。
6.根据权利要求1所述的一种MOF基二维超薄电催化剂的制备方法,其特征在于,步骤S2中,所述铁盐包括氯化亚铁和硫酸亚铁,所述钴盐包括氯化钴,所述锰盐包括氯化锰。
7.根据权利要求1-6任一项所述的方法制备的MOF基二维超薄电催化剂。
8.权利要求7所述的MOF基二维超薄电催化剂在电解水中的应用。
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