CN108745381B - 以mof为基底制备硫化钴催化剂的方法 - Google Patents
以mof为基底制备硫化钴催化剂的方法 Download PDFInfo
- Publication number
- CN108745381B CN108745381B CN201810577273.0A CN201810577273A CN108745381B CN 108745381 B CN108745381 B CN 108745381B CN 201810577273 A CN201810577273 A CN 201810577273A CN 108745381 B CN108745381 B CN 108745381B
- Authority
- CN
- China
- Prior art keywords
- mof
- cos
- cobalt sulfide
- preparing
- atmosphere
- 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 27
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 title claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 23
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000004073 vulcanization Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 2
- HVVTZHOQYOYMES-UHFFFAOYSA-N ethanol 4-pyridin-4-ylpyridine Chemical compound CCO.C1=NC=CC(C=2C=CN=CC=2)=C1 HVVTZHOQYOYMES-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000013259 porous coordination polymer Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical class [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 2
- 229910002463 CoxSy Inorganic materials 0.000 description 1
- 241000978750 Havardia Species 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了以MOF为基底制备硫化钴催化剂的方法,通过调节不同煅烧时间和气氛以及原位硫化法制备的四种以MOF为前驱体的硫化钴催化剂,Co‑MOF自身含有硫和氮元素,可以不在外加硫源的条件下原位硫化,并且通过调节不同煅烧时间和气氛,利用硫在高温下升华的特点,制备出四种硫化钴,分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO。其中复合相Co9S8&CoS1.097/rGO具有很好的酸性条件下电催化产氢的性质。本发明提供的制备方法安全并且简单易行,是理想的电催化产氢催化剂。
Description
技术领域
本发明涉及电解水产氢催化剂技术领域,具体涉及通过调节不同煅烧时间和气氛以及原位硫化法制备的四种以MOF为前驱体的CoxSy催化剂,分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO
背景技术
金属-有机框架(Metal-Organic Framework,MOFs),又称为多孔配位聚合物(Porous CoordinationPolymers,PCPs),是由金属离子或金属簇与有机配体通过配位键形成的一类具有周期性网络结构的晶态多孔框架材料,因其高比表面积、多孔、结构可调等特性,在气体的吸附分离、催化、传感和质子传导等方面具有潜在的应用前景。参见:Nandasiri,M.I.;Jambovane,S.R.;McGrail,B.P.;Schaef,H.T.;Nune,S.K.Coord.Chem.Rev.2016,311,38-52;H.Furukawa,N.Ko,Y.B.Go,N.Aratani,S.B.Choi,E.Choi,A.Yazaydin,R.Q.Snurr,M.O'Keeffe,J.Kim,O.M.Yaghi,Science 2010,329,424.随着社会发展,对化石燃料的需求不断增加,随之而来的环境污染也不断加剧,如何在发展经济的同时保护自然环境成为亟待解决的问题。氢能因其环境友好性和高的能量密度成为未来有潜力替代化石能源的重要清洁能源。近年来,科研人员致力于探索将地球丰度高的过渡金属化合物发展成活性高的电催化分解水产氢催化剂以替代贵金属催化剂。金属有机框架材料(MOFs)的结构具有可调整、可修饰和易功能化等特点,使其在磁性、储存、分离、催化和识别等方面表现出广阔的应用前景。其次,以它们作为前驱体构筑碳基催化材料,在杂原子掺杂、粒子限域以及孔道设计方面具有独特的优势。参见:Yu,M.H.;Zhang,P.;Feng,R.;Yao,Z.Q.;Yu,Y.C.;Hu,T.L.;Bu,X.H.ACS Appl.Mater.Interfaces,2017,9:26177;Chang,Z.;Yang,D.H.;Xu,J;Hu,T.L.;Bu,X.H.Adv.Mater.,2015,27,5432;Zhong,M.;Yang,D.H.;Xie,C.C.;Zhang,Z.;Zhou,Z.;Bu,X.H.Small,2016,12,5564.
发明内容
本发明的目的在于探索以MOF为基底制备硫化钴催化剂的方法,同时也提供了一种通过改变煅烧时间和煅烧气氛制备不同复合物的方法。制得的四种硫化钴分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO。
本发明的技术方案:
以MOF为基底制备硫化钴催化剂的方法,通过MOF原位硫化法制备硫化钴电解水产氢催化剂,通过调节不同煅烧时间和气氛以及通过MOF原位硫化法制备硫化钴催化剂。
四种CoxSy的制备方法,包括以下步骤:
Co-MOF:硫氰酸钴溶于去离子水,4,4-联吡啶溶于乙醇溶液,室温下搅拌下,将4,4-联吡啶乙醇溶液滴加到硫氰酸钴水溶液中,即可得到。
CoS1.097:Co-MOF氩气气氛下700℃煅烧一小时。
Co9S8&CoS1.097:Co-MOF氩气气氛下700℃煅烧两个小时。
Co9S8:Co-MOF氩氢混合气气氛下700℃煅烧两个小时。
Co9S8&CoS1.097/rGO:Co-MOF与氧化石墨烯结合后,氩气气氛下700℃煅烧两个小时。
有益效果:
1.本发明在MOF的选择上,选择一个自身含有S和N的Co-MOF,通过煅烧可以通过原位硫化法直接生成硫化钴,不需要外加硫源。
2.本发明可以通过调节煅烧时间和煅烧气氛,利用高温下硫的升华使得S含量不同,从而得到不同的硫化钴复合物。
3.通过加入石墨烯,提高材料导电性,防止煅烧过程中MOF的团聚从而使得电催化性能进一步提高复合相其电催化性能达到起始电位50mV,当电流密度达到10mA cm-2时过电位为188mV。
附图说明
图1为制备流程图。
图2为Co9S8&CoS1.097/rGO的扫描电镜、透射电镜、高分辨透射电镜图。
图3为Co-MOF、CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO的粉末衍射图以及Co9S8&CoS1.097/rGO的X射线光电子能谱。
图4为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO的孔径分布图。
图5为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO电催化性能图。
具体实施方式
本发明具体涉及通过调节不同煅烧时间和气氛以及原位硫化法制备的四种以MOF为前驱体的硫化钴催化剂,分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO,制备流程参见附图1。下面结合附图与实施例对本发明做进一步说明。
1.0.326g Co(SCN)2溶于20mL去离子水,0.63g 4’4-联吡啶溶于30mL乙醇溶液室温下边搅拌边将4’4-联吡啶乙醇溶液逐滴加入到Co(SCN)2水溶液中,离心得到粉晶Co-MOF,所得Co-MOF的粉末衍射图见附图3(a)。
2.0.2g Co-MOF放入管式炉中氩气气氛下700℃煅烧一小时得到CoS1.097;氩气气氛下700℃煅烧两个小时,得到Co9S8&CoS1.097;氩氢混合气气氛下700℃煅烧2h得到Co9S8
3.20mL去离子水中加入100mg氧化石墨烯超声30min,搅拌30min至均匀分散,边搅拌边滴加Co(SCN)2水溶液(0.326g,2mL)。搅拌1h后,边搅拌边滴加4’4-联吡啶乙醇溶液(0.63g,30mL)。搅拌10min,得到Co-MOF/GO,其粉末衍射图见附图3(a)。取0.2g放入管式炉中,氩气气氛下700℃煅烧2h得到Co9S8&CoS1.097/rGO。
参见附图2,a为扫描电镜图,b为a的区域放大扫描电镜图,从扫描电镜图中可以看出Co-MOF生成的复合相Co9S8&CoS1.097均匀的附着在石墨烯表面。c、d为透射电镜图。从透射电镜图中可以观察到许多小于10nm纳米颗粒附着在石墨烯上。e为块状Co9S8&CoS1.097高分辨透射电镜图,从晶格条纹可以进一步证明块状为复合相Co9S8&CoS1.097,f为纳米颗粒高分辨电镜图,从晶格条纹可以证明,该纳米颗粒为Co9S8。
参见图3,Co-MOF以及所得四种催化剂CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO的粉末衍射图见附图3(a)(b)与标准卡片都可以很好的对应上;证明合成的相纯度高。Co9S8&CoS1.097/rGO的X射线光电子能谱参见,(c)-(f)。从图中可以看出,该材料的碳层有许多S、N杂原子掺杂,并且N元素主要以石墨N和吡啶N的形式存在,进一步提高了其电催化性能。S元素xps图中有两组S元素的P峰,进一步证明其由两相组成。
参见附图4,从孔径分布图中可以看出,石墨烯的加入防止了Co-MOF在煅烧过程中的团聚,从而增大了比表面积和孔径。
参见附图5,a为在0.5MH2SO4水溶液中以5mV s-1扫速得到的产氢极化曲线,从图中可以看出与石墨烯的复合相Co9S8&CoS1.097/rGO性能最好,当电流达到10mA cm-2时,电位仅为381mV。b图为tafel曲线图,从图中可以看出复合相Co9S8&CoS1.097/rGO的tafel斜率虽然比CoS1.097大,但是和其他相相比较小,说明其电催化产氢反应动力学较快。c图为循环1000全之后极化曲线,可以看出该材料稳定性很好,极化曲线偏移很小。d图为电流密度差-扫速曲线,从中可以看出复合相的双电层电容最大,证明其电化学活性面积最大。综合以上测试可以证明与石墨烯复合相Co9S8&CoS1.097/rGO的电催化产氢性能最好。
Claims (3)
1.以MOF为基底制备硫化钴催化剂的方法,其特征在于:通过MOF原位硫化法制备硫化钴电解水产氢催化剂,通过调节不同煅烧时间和气氛以及通过MOF原位硫化法制备硫化钴催化剂;
所述的硫化钴催化剂分别为CoS1.097,Co9S8和Co9S8&CoS1.097;
CoS1.097是由Co-MOF氩气气氛下700℃煅烧一小时得到;
Co9S8&CoS1.097是由Co-MOF氩气气氛下700℃煅烧两个小时得到;
Co9S8是由Co-MOF氩氢混合气气氛下700℃煅烧两个小时得到;
Co-MOF制备步骤是:硫氰酸钴溶于去离子水,4,4-联吡啶溶于乙醇溶液,室温下搅拌下,将4,4-联吡啶乙醇溶液滴加到硫氰酸钴水溶液中,即可得到。
2.以MOF为基底制备硫化钴催化剂的方法,其特征在于:通过MOF原位硫化法制备硫化钴电解水产氢催化剂,通过调节不同煅烧时间和气氛以及通过MOF原位硫化法制备硫化钴催化剂;
所述的硫化钴催化剂为Co9S8&CoS1.097/rGO;
Co9S8&CoS1.097/rGO是由Co-MOF与氧化石墨烯结合后得到Co-MOF/GO,氩气气氛下700℃煅烧两个小时得到;
Co-MOF/GO是在去离子水中加入氧化石墨烯超声30min,搅拌30min 至均匀分散,边搅拌边滴加Co(SCN)2水溶液,搅拌1h后,边搅拌边滴加4’4-联吡啶乙醇溶液,搅拌10min得到Co-MOF/GO。
3.根据权利要求2所述的以MOF为基底制备硫化钴催化剂的方法,其特征在于:所得硫化钴催化剂起始电位50mV,当电流密度达到10mA cm-2时过电位为188mV,并且具有很好的稳定性。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810577273.0A CN108745381B (zh) | 2018-06-07 | 2018-06-07 | 以mof为基底制备硫化钴催化剂的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810577273.0A CN108745381B (zh) | 2018-06-07 | 2018-06-07 | 以mof为基底制备硫化钴催化剂的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108745381A CN108745381A (zh) | 2018-11-06 |
CN108745381B true CN108745381B (zh) | 2020-10-09 |
Family
ID=63999238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810577273.0A Active CN108745381B (zh) | 2018-06-07 | 2018-06-07 | 以mof为基底制备硫化钴催化剂的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108745381B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109759115A (zh) * | 2019-02-11 | 2019-05-17 | 郑州大学 | 纳米钴/硫化钴负载于杂原子掺杂的多孔碳复合型催化剂及其制备方法和应用 |
CN111450898B (zh) * | 2020-05-18 | 2021-12-21 | 安徽工业大学 | 光催化降解有机染料的无定形CoSx/MOF复合催化剂及制备方法 |
CN111468164B (zh) * | 2020-05-22 | 2021-10-15 | 庄秀萍 | 一种氮掺杂纳米ZnS/石墨烯光催化材料的制备方法及应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106450200A (zh) * | 2016-10-25 | 2017-02-22 | 福建师范大学 | 一种CoS@碳纳米笼及其制备方法和应用 |
CN106531999A (zh) * | 2016-11-25 | 2017-03-22 | 武汉理工大学 | 嵌入式硫化钴与多孔碳纳米棒复合电极材料及其制备方法和应用 |
KR20170043138A (ko) * | 2015-10-12 | 2017-04-21 | 한양대학교 에리카산학협력단 | MOF(Metal Organic Framework) 기반의 코발트 황화물의 제조 방법, 및 이를 이용한 염료감응형 태양전지 |
CN107321372A (zh) * | 2017-06-06 | 2017-11-07 | 江苏大学 | CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法 |
-
2018
- 2018-06-07 CN CN201810577273.0A patent/CN108745381B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170043138A (ko) * | 2015-10-12 | 2017-04-21 | 한양대학교 에리카산학협력단 | MOF(Metal Organic Framework) 기반의 코발트 황화물의 제조 방법, 및 이를 이용한 염료감응형 태양전지 |
CN106450200A (zh) * | 2016-10-25 | 2017-02-22 | 福建师范大学 | 一种CoS@碳纳米笼及其制备方法和应用 |
CN106531999A (zh) * | 2016-11-25 | 2017-03-22 | 武汉理工大学 | 嵌入式硫化钴与多孔碳纳米棒复合电极材料及其制备方法和应用 |
CN107321372A (zh) * | 2017-06-06 | 2017-11-07 | 江苏大学 | CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法 |
Non-Patent Citations (4)
Title |
---|
Coordination Polymers of Co(NCS)2 with Pyrazine and 4,4’-Bipyridine: Syntheses and Structures;Jian Lu et al.;《Inorg. Chem.》;19971231;第924页左栏最后1段 * |
S,N-Containing Co-MOF derived Co9S8@S,N-doped carbon materials as efficient oxygen electrocatalysts and supercapacitor electrode materials;Shengwen Liu et al.;《Inorganic Chemistry Frontiers》;20171227;第491页摘要和第492页实验部分 * |
Shengwen Liu et al..S,N-Containing Co-MOF derived Co9S8@S,N-doped carbon materials as efficient oxygen electrocatalysts and supercapacitor electrode materials.《Inorganic Chemistry Frontiers》.2017, * |
Zeolitic imidazole framework derived composites of nitrogen-doped porous carbon and reduced graphene oxide as high-efficiency cathode catalysts for Li–O2 batteries;Ming Zhong et al.;《Inorganic Chemistry Frontiers》;20170714;第1533页摘要和第1534页实验部分 * |
Also Published As
Publication number | Publication date |
---|---|
CN108745381A (zh) | 2018-11-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Two-dimensional NiSe2/N-rich carbon nanocomposites derived from Ni-hexamine frameworks for superb Na-ion storage | |
Guo et al. | CoMo carbide/nitride from bimetallic MOF precursors for enhanced OER performance | |
Abazari et al. | Mixed metal Fe2Ni MIL-88B metal–organic frameworks decorated on reduced graphene oxide as a robust and highly efficient electrocatalyst for alkaline water oxidation | |
Li et al. | ZIF-67 as continuous self-sacrifice template derived NiCo2O4/Co, N-CNTs nanocages as efficient bifunctional electrocatalysts for rechargeable Zn–air batteries | |
Li et al. | Ultralow Ru-induced bimetal electrocatalysts with a Ru-enriched and mixed-valence surface anchored on a hollow carbon matrix for oxygen reduction and water splitting | |
Ding et al. | N-doped 3D porous Ni/C bifunctional electrocatalysts for alkaline water electrolysis | |
Javaid et al. | Ni2+/Co2+ doped Au-Fe7S8 nanoplatelets with exceptionally high oxygen evolution reaction activity | |
Madhu et al. | Electrospun cobalt-incorporated MOF-5 microfibers as a promising electrocatalyst for OER in alkaline media | |
Fan et al. | Phosphorus-doped FeNi alloys/NiFe2O4 imbedded in carbon network hollow bipyramid as efficient electrocatalysts for oxygen evolution reaction | |
CN108745381B (zh) | 以mof为基底制备硫化钴催化剂的方法 | |
Li et al. | Ni (OH) 2 microspheres in situ self-grown on ultra-thin layered g-C3N4 as a heterojunction electrocatalyst for oxygen evolution reaction | |
Sundararaj et al. | Layered porous graphitic carbon nitride stabilized effective Co2SnO4 inverse spinel as a bifunctional electrocatalyst for overall water splitting | |
Kumar et al. | A superior and stable electrocatalytic oxygen evolution reaction by one-dimensional FeCoP colloidal nanostructures | |
Sun et al. | Exploiting a high-performance “double-carbon” structure Co9S8/GN bifunctional catalysts for rechargeable Zn–air batteries | |
Lu et al. | Metal organic frameworks derived CoSe2@ N-Doped-carbon-nanorods as highly efficient electrocatalysts for oxygen evolution reaction | |
Cui et al. | Promotion of the electrocatalytic oxygen evolution reaction by chemical coupling of CoOOH particles to 3D branched γ-MnOOH rods | |
Fang et al. | Bimetallic NiFe 2 O 4 synthesized via confined carburization in NiFe-MOFs for efficient oxygen evolution reaction | |
Li et al. | Amorphous yolk–shelled ZIF-67@ Co3 (PO4) 2 as nonprecious bifunctional catalysts for boosting overall water splitting | |
Shen et al. | Fabrication of 2D/3D hierarchical PBA and derivative electrocatalysts for overall water splitting | |
Miao et al. | In situ self-assembly-generated 3D hierarchical Co3O4 micro/nanomaterial series: selective synthesis, morphological control, and energy applications | |
Singu et al. | Development of metal-organic framework-derived NiMo-MoO3− x porous nanorod for efficient electrocatalytic hydrogen evolution reactions | |
Wang et al. | Gallium oxynitride@ carbon cloth with impressive electrochemical performance for supercapacitors | |
Zhang et al. | Deep eutectic solvent-mediated hierarchically structured Fe-based organic–inorganic hybrid catalyst for oxygen evolution reaction | |
Arunkumar et al. | Impact of an incompatible atomic nickel-incorporated metal–organic framework on phase evolution and electrocatalytic activity of Ni-doped cobalt phosphide for the hydrogen evolution reaction | |
Wang et al. | Hybrid cobalt-based electrocatalysts with adjustable compositions for electrochemical water splitting derived from Co2+-Loaded MIL-53 (Fe) particles |
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 | ||
EE01 | Entry into force of recordation of patent licensing contract | ||
EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20181106 Assignee: TIANJIN QUANHECHENG TECHNOLOGY Co.,Ltd. Assignor: NANKAI University Contract record no.: X2024980002700 Denomination of invention: A Method for Preparing Cobalt Sulfide Catalysts Based on MOFs Granted publication date: 20201009 License type: Common License Record date: 20240312 |