CN111871406B - 一种电化学还原二氧化碳制合成气的催化剂及其制备方法 - Google Patents
一种电化学还原二氧化碳制合成气的催化剂及其制备方法 Download PDFInfo
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- CN111871406B CN111871406B CN202010786100.7A CN202010786100A CN111871406B CN 111871406 B CN111871406 B CN 111871406B CN 202010786100 A CN202010786100 A CN 202010786100A CN 111871406 B CN111871406 B CN 111871406B
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- 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
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- CODVACFVSVNQPY-UHFFFAOYSA-N [Co].[C] Chemical compound [Co].[C] CODVACFVSVNQPY-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
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- 239000011715 vitamin B12 Substances 0.000 description 1
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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Abstract
本发明涉及一种电化学还原二氧化碳制合成气的催化剂及其制备方法与其在二氧化碳电化学还原中的应用，属于二氧化碳资源化利用和储能技术领域。该催化剂由含金属原子M1的层级孔结构的碳载体负载含金属原子M2的分子催化剂制得。所述的碳载体，由金属离子交联的聚乙烯基咪唑结合二氧化硅纳米球硬模板高温碳化后，经碱洗制得，然后负载分子催化剂。本发明的催化剂，通过改变载体和分子催化剂中金属中心原子的种类实现对氢析出反应和二氧化碳还原反应的选择性进行调控，并结合电解液和电位的改变实现对生成的合成气中H2/CO的比例调变。该方法具有良好的适用性，操作简单易于放大生产，具有良好的应用前景。
Description
技术领域
本发明涉及一种电化学还原二氧化碳制合成气的催化剂及其制备方法与其在二氧化碳电化学还原中的应用，属于二氧化碳资源化利用和储能技术领域。
背景技术
二氧化碳（CO2）的资源化利用是缓解日益严峻的能源短缺和环境污染问题的重要手段。其中，可持续能源驱动的电化学还原将CO2转化为高附加值的化学品和燃料成为一种备受瞩目的技术。然而，随着反应条件的改变，CO2可还原成多种化合物，包括一氧化碳（CO）、甲酸（HCOOH）、乙酸（CH3COOH）、甲烷（CH4）、乙烯（C2H4）、甲醇（CH3OH）和乙醇（CH3CH2OH）等，这就使得高选择性地制备某一产物，尤其是C2+物质，变得十分困难。另一方面，由于水系电解液中CO2分子的溶解度较低，使得产生单一产物的电流密度较低而无法实际应用。鉴于此，利用水系电解液体系中不可避免的氢析出反应（HER）产生的氢气（H2），结合CO2还原生成CO从而得到具有不同H2和CO比例（H2/CO）的合成气成为另一种更具有可行性的路径。考虑到合成气在工业生产中的广泛用途，以及现有的较为成熟的基于合成气的生产工艺，该路径具有适用性强、生产线搭建简单以及成本低等优势。
实现高效CO2还原生产合成气的关键是设计同时具有CO2还原和HER活性的双功能催化剂，并结合活性组分的调节和电解液的设计实现高电流密度下制备具有宽的H2/CO比例的合成气。目前，基于贵金属的催化剂如金（Au），或其它金属的合金催化剂虽能实现合成气H2/CO的调控，但其电流密度仍较低。同时，金属硫属化合物也展现了良好的催化CO2转化为合成气的能力，但其制备过程难以放大和规模化生产，制约了实际应用（Angew. Chem.Int. Ed. 2017， 129， 9249-9253）。另一方面，杂原子掺杂的碳材料作为CO2还原的催化剂受到了广泛的关注，尤其是单原子金属位点掺杂的碳材料展现了优异的CO选择性。该类材料的组分以及孔结构的可设计性提供了还原产物和电流密度的可调控性。鉴于此，开发一套高效产生合成气的双功能碳基单原子催化剂并简化其制备方法具有十分广阔的应用前景。
发明内容
为解决上述技术问题，本发明开发了一种具有CO2还原和HER活性的双功能催化剂，本发明的催化剂由单M1金属掺杂的碳载体负载含M2金属的分子催化剂制得，所述的含单M1原子的碳载体是以M1金属离子和锌离子交联的聚乙烯基咪唑为前驱体，在惰性气氛下碳化得到。本发明同时提供了该催化剂的制备方法，该方法简单易操作，适合工业化生产。最后将其用于二氧化碳电化学还原，可在高电流密度下制备具有宽范围的H2/CO比例的合成气。
本发明采用的技术方案如下：
一种电化学还原二氧化碳制备合成气的催化剂，所述的催化剂由含单金属原子M1的碳载体负载含金属原子M2的分子催化剂组成；所述的M1原子为铁、钴、镍、铜、锌、铝、铬、锰、银、钌、铟、锡、铋中的一种或多种。
优选地，所述含原子M2的分子催化剂为铁、钴、铜、锰中一种或多种的酞菁、卟啉或维生素B12的分子催化剂。
优选地，所述的含单原子M1的碳载体上M1的含量为0.5-2.0 wt%；所述的单原子M1的碳载体与负载的分子催化剂的质量比为：10:1-1:10。
优选地，所述的含单原子M1的碳载体，由金属离子交联的聚乙烯基咪唑结合二氧化硅纳米球硬模板高温碳化后，经碱洗制得。
优选地，所述的高温碳化的温度为910-1050 oC，时间为1-4 h，反应气氛为氩气。
上述电化学还原二氧化碳制备合成气的催化剂的制备方法，采用湿法高温处理或物理混合的方式负载分子催化剂。
优选地，所述的湿法高温处理以N，N-二甲基甲酰胺为溶剂；所述物理混合方式包括研磨和球磨。
上述制备方法制备的催化剂在电化学还原CO2制备合成气中的应用，所述的催化剂作为催化电极参与电化学还原CO2制备合成气；所述的催化电极的制备过程为：将催化剂粉末与Nafion粘结剂在分散剂中超声分散后直接滴涂于碳纸并烘干。
优选地，所述的分散剂为乙醇、异丙醇、乙二醇中的一种或几种与水的混合物；所述Nafion粘结剂与分散剂的体积比为1：19；所述催化剂浆料中催化剂浓度为1-10 mg/mL；所述的烘干温度为50-100 oC。
本发明所提供的催化剂在三电极体系中进行电化学测试：负载催化剂的电极为工作电极，Pt网为对电极，Ag/AgCl为参比电极。电解液为KHCO3水溶液。所述电解池包括H型双室电解液和流动型电解池。所述电解液浓度为0.1至1 M。
本发明提供的单M1原子碳载体以金属离子交联的聚乙烯基咪唑为前驱体，在惰性气氛下碳化得到，具体方法为：乙烯基咪唑在偶氮二异丁腈引发下发生聚合，溶剂为N，N-二甲基甲酰胺，反应后制得聚乙烯基咪唑，将其溶于乙醇后与二氧化硅纳米球混合，然后与相应金属离子的乙醇溶液混合得到交联聚乙烯基咪唑前驱体。该前驱体在氩气气氛下于管式炉中进行碳化，然后在浓碱溶液中处理除去二氧化硅纳米球，洗涤、烘干后得到单M1原子碳载体。
本发明提供的碳基单原子催化剂由单M1金属碳载体负载含M2金属的分子催化剂制得，其制备方法分为两种：一种是一定比例的碳载体与分子催化剂分散在N，N-二甲基甲酰胺中，于90 oC下处理后除去溶剂并烘干；另一种是一定比例的碳载体与分子催化剂直接物理混合。本发明提供的CO2还原催化电极的制备如下：将单M1原子碳载体负载的M2分子催化剂加入分散剂，加入Nafion粘结剂后超声振荡分散均匀得到催化剂浆料；将浆料涂敷在碳纸上并烘干后得到催化电极。
本发明公开了一种用于二氧化碳电还原制备具有不同H2/CO比例合成气的碳基单金属原子催化剂及其制备方法。该催化剂由含金属原子M1的层级孔结构的碳载体负载含金属原子M2的分子催化剂制得。所述单原子M1的碳载体通过高温碳化金属离子交联的聚乙烯基咪唑制备，结合二氧化硅纳米球硬模板得到同时具有大孔、介孔和微孔的碳载体。该载体通过简便的物理混合等方式与分子催化剂结合后可直接作为二氧化碳电还原催化剂。
本发明的有益效果
1、在较宽的范围内对生成的合成气中H2/CO的比例进行调变
本发明提供的催化剂，可通过改变载体和分子催化剂中金属中心原子的种类实现对氢析出反应和二氧化碳还原反应的选择性进行调控，结合电解液和电位的改变实现在较宽的范围内对生成的合成气中H2/CO的比例进行调变，得到H2/CO比例为0.2至30的合成气，并在高电流密度下得到可直接用于费托合成的具有理想H2/CO比例的合成气（如在H型电解池中以高于220 mA cm-2的电流密度得到H2/CO比例为3的合成气）。
2、适用性好，适合工业化
该方法对多种金属离子具有良好的适用性，且原料价廉、来源广，操作简单易于放大生产，在电化学二氧化碳制合成气及其它领域将具有良好的应用前景。
附图说明
图1为本发明实施例1中单原子Co碳载体的扫描电镜和氮气吸脱附测试得到的孔尺寸分布曲线（图1a）以及球差校正透射电镜图（图1b）。
图2为实施例2中的催化电极在不同电位下的总电流密度（图2a）和还原产物中H2/CO比例（图2b）。
图3为实施例3中的催化电极在不同电位下的总电流密度（图3a）和还原产物中H2/CO比例（图3b）。
图4为实施例4中的催化电极在不同电位下的总电流密度（图4a）和还原产物中H2/CO比例（图4b）。
图5为实施例5中的催化电极在不同电位下的总电流密度（图5a）和还原产物中H2/CO比例（图5b）。
图6为实施例6中的催化电极在不同电位下的总电流密度（图6a）和还原产物中H2/CO比例（图6b）。
图7为实施例7中的催化电极在不同电位下的总电流密度（图7a）和还原产物中H2/CO比例（图7b）。
图8为实施例8中的催化电极在不同电位下的总电流密度（图8a）和还原产物中H2/CO比例（图8b）。
具体实施方式：
为了更好地理解本发明，下面结合实施例进一步进行阐述，但这些实施例不应理解为对本发明的任何限制。
实施例1 单原子Co碳载体（SACo-C）的制备
0.25 g 聚乙烯基咪唑溶于10 mL乙醇中，加入1 g的二氧化硅纳米球，超声振荡30min后，将20 mL含0.126 g 硝酸锌和0.0051 g 硝酸钴的乙醇溶液缓慢滴入，室温搅拌2 h后离心并在80度干燥12 h得到粉红色固体粉末。将所得固体粉末置于瓷舟中，在管式炉中氩气气氛下950 oC碳化2 h，气体流速为20 sccm。将碳化后所得黑色固体粉末在30 mL 2 MKOH溶液中80 oC反应24 h，冷却后过滤并洗涤至中性，80 oC下干燥后得到钴负载量为0.61wt%的单原子钴碳载体。
如图1a所示，扫描电镜证实了大孔的存在，而氮气吸脱附实验表明了微、介孔的存在。球差校正的透射电子显微镜证实了Co的原子级分散（图1b）。
实施例2
电化学还原二氧化碳制备合成气的催化剂的制备方法，包括以下步骤：
（1）取2 mg酞菁钴（CoPc，分子催化剂）溶于60 mL N，N-二甲基甲酰胺中，然后加入20 mg SACo-C（实施例1制备得到），在90 oC下处理24 h后旋蒸除去溶剂，并在80 oC下烘干得到SACo-C/CoPc(10:1)。
（2）取5 mg SACo-C/CoPc(10:1)加入950 μL乙醇和50 μL Nafion溶液（5 wt%）中，超声振荡60 min后取200 μL浆料滴涂于1*1 cm2的正方形碳纸上，在80 oC下烘干后得到负载量为1 mg cm-2的催化电极。
在1 M KHCO3溶液中采用H型电解池评价CO2电还原性能。如图2所示，最大的电解电流可达到220 mA cm-2，并且在H2/CO接近2和3时的最大电流为84 mA cm-2和148 mA cm-2。
实施例3
电化学还原二氧化碳制备合成气的催化剂的制备方法，包括以下步骤：
（1）取4 mg酞菁钴（CoPc，分子催化剂）溶于120 mL N，N-二甲基甲酰胺中，然后加入20 mg SACo-C（实施例1制备得到），在90 oC下处理24 h后旋蒸除去溶剂，并在80 oC下烘干得到SACo-C/CoPc(5:1)。
（2）取5 mg SACo-C/CoPc(5:1)加入950 μL乙醇和50 μL Nafion溶液（5 wt%）中，超声振荡60 min后取200 μL浆料滴涂于1*1 cm2的正方形碳纸上，在80 oC下烘干后得到负载量为1 mg cm-2的催化电极。
在0.5 M KHCO3溶液中采用H型电解池评价CO2电还原性能。如图3所示，最大的电解电流可达到180 mA cm-2，并且在H2/CO接近1和2时的最大电流为112 mA cm-2和180 mA cm-2。
实施例4
实施例3中制备的SACo-C/CoPc(5:1)电极在1 M KHCO3溶液中采用H型电解池评价CO2电还原性能。如图4所示，最大的电解电流可达到225 mA cm-2，并且在H2/CO接近2和3时的最大电流为132 mA cm-2和225 mA cm-2。
实施例5
电化学还原二氧化碳制备合成气的催化剂的制备方法，包括以下步骤：
（1）取10 mg酞菁钴（CoPc，分子催化剂）与10 mg SACo-C（实施例1制备得到）在玛瑙研钵中直接研磨混合，得到SACo-C/CoPc(1:1)。
（2）取5 mg SACo-C/CoPc(1:1)加入950 μL乙醇和50 μL Nafion溶液（5 wt%）中，超声振荡60 min后取200 μL浆料滴涂于1*1 cm2的正方形碳纸上，在80 oC下烘干后得到负载量为1mg cm-2的催化电极。
在0.1 M KHCO3溶液中采用H型电解池评价CO2电还原性能。如图5所示，最大的电解电流可达到116 mA cm-2，并且在H2/CO接近2和3时的最大电流为29 mA cm-2和80 mA cm-2。
实施例6
实施例5中制备的SACo-C/CoPc(1:1)电极在0.5 M KHCO3溶液中采用H型电解池评价CO2电还原性能。如图6所示，最大的电解电流可达到144 mA cm-2，并且在H2/CO接近1和2时的最大电流为100 mA cm-2和144 mA cm-2。
实施例7单原子Cu-碳载体（SACu-C）的制备
0.25 g 聚乙烯基咪唑溶于10 mL乙醇中，加入1 g的二氧化硅纳米球，超声振荡30min后，将20 mL含0.126 g 硝酸锌和0.0032 g 硝酸铜的乙醇溶液缓慢滴入，室温搅拌2 h后离心并在80度干燥12 h得到淡蓝色固体粉末。将所得固体粉末置于瓷舟中，在管式炉中氩气气氛下950 oC碳化2 h，气体流速为20 sccm。将碳化后所得黑色固体粉末在30 mL 2 MKOH溶液中80 oC反应24 h，冷却后过滤并洗涤至中性，80 oC下干燥后得到铜含量为0.72wt%的单原子铜碳载体。
采用实施例2中的方法制备SACu-C/CoPc(10:1)催化电极，在1 M KHCO3中采用流动池评价CO2电还原性能。如图7所示，最大的电解电流可达到410 mA cm-2，并且在H2/CO接近1时的最大电流为240 mA cm-2。
实施例8单原子Cr-碳载体（SACr-C）的制备
0.25 g 聚乙烯基咪唑溶于10 mL乙醇中，加入1 g的二氧化硅纳米球，超声振荡30min后，将20 mL含0.126 g 硝酸锌和0.0069 g 硝酸铬的乙醇溶液缓慢滴入，室温搅拌2 h后离心并在80度干燥12 h得到淡绿色固体粉末。将所得固体粉末置于瓷舟中，在管式炉中氩气气氛下950 oC碳化2 h，气体流速为20 sccm。将碳化后所得黑色固体粉末在30 mL 2 MKOH溶液中80 oC反应24 h，冷却后过滤并洗涤至中性，80 oC下干燥后得到铬负载量为0.55wt%的单原子铬碳载体。
采用实施例3的方法制备SACr-C/CoPc(5:1)催化电极，在1 M KHCO3中采用流动池评价CO2电还原性能。如图8所示，最大的电解电流可达到580 mA cm-2，并且在H2/CO接近2和1时的最大电流为97和580 mA cm-2。
Claims (6)
1.一种电化学还原二氧化碳制备合成气的催化剂，其特征在于，所述的催化剂由含单原子M1的碳载体负载含金属原子M2的分子催化剂组成；M1为铜、铬、钴中的一种；
所述含金属原子M2的分子催化剂为铁、钴、铜、锰中一种或多种的酞菁或卟啉的分子催化剂；
所述的含单原子M1的碳载体的具体制备方法为：乙烯基咪唑在偶氮二异丁腈引发下发生聚合，溶剂为N，N-二 甲基甲酰胺，反应后制得聚乙烯基咪唑，将其溶于乙醇后与二氧化硅纳米球混合，然后与硝酸铜、硝酸钴、硝酸铬中的一种的乙醇溶液和硝酸锌的乙醇溶液混合得到交联聚乙烯基咪唑前驱体；该前驱体在氩气气氛下于管式炉中进行碳化，然后在浓碱溶液中处理除去二氧化硅纳米球，洗涤、烘干；
所述的含单原子M1的碳载体与负载的分子催化剂的质量比为：10:1-1:10；
所述的碳化的温度为910-1050 ℃，反应气氛为氩气。
2.权利要求1所述的电化学还原二氧化碳制备合成气的催化剂的制备方法，其特征在于，采用物理混合的方式负载分子催化剂。
3.如权利要求2所述的制备方法，其特征在于，所述物理混合方式为研磨。
4.采用权利要求2所述的制备方法得到的催化剂在电化学还原CO2制备合成气中的应用，其特征在于，所述的催化剂作为催化电极参与电化学还原CO2制备合成气；所述的催化电极的制备过程为：将催化剂粉末与Nafion粘结剂在分散剂中超声分散后直接滴涂于碳纸并烘干。
5. 如权利要求4所述的应用，其特征在于，所述的分散剂为乙醇、异丙醇、乙二醇中的一种或多种与水的混合物；所述Nafion粘结剂与分散剂的体积比为1：19；催化剂浆料中催化剂浓度为1-10 mg/mL。
6.如权利要求4所述的应用，其特征在于，所述的烘干温度为50-100℃。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944746A (zh) * | 2016-05-18 | 2016-09-21 | 中国科学院理化技术研究所 | 一种碳负载氮化镍催化剂及其制备方法和应用 |
| WO2018132937A1 (en) * | 2017-01-17 | 2018-07-26 | South University Of Science And Technology Of China | Use of metal phthalocyanine/nanocarbon hybrid catalysts for efficient electrochemical reduction of co2 |
| CN109494381A (zh) * | 2017-09-12 | 2019-03-19 | 中国科学院大连化学物理研究所 | 一种单原子铁基碳材料及制备方法和电催化应用 |
| CN109675603A (zh) * | 2018-12-28 | 2019-04-26 | 西安交通大学 | 一种二氧化硅保护的碳基催化剂及其制备方法和应用 |
| CN110295375A (zh) * | 2019-06-20 | 2019-10-01 | 中国科学院青岛生物能源与过程研究所 | 一种电还原co2催化剂的制备及催化剂和应用 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944746A (zh) * | 2016-05-18 | 2016-09-21 | 中国科学院理化技术研究所 | 一种碳负载氮化镍催化剂及其制备方法和应用 |
| WO2018132937A1 (en) * | 2017-01-17 | 2018-07-26 | South University Of Science And Technology Of China | Use of metal phthalocyanine/nanocarbon hybrid catalysts for efficient electrochemical reduction of co2 |
| CN109494381A (zh) * | 2017-09-12 | 2019-03-19 | 中国科学院大连化学物理研究所 | 一种单原子铁基碳材料及制备方法和电催化应用 |
| CN109675603A (zh) * | 2018-12-28 | 2019-04-26 | 西安交通大学 | 一种二氧化硅保护的碳基催化剂及其制备方法和应用 |
| CN110295375A (zh) * | 2019-06-20 | 2019-10-01 | 中国科学院青岛生物能源与过程研究所 | 一种电还原co2催化剂的制备及催化剂和应用 |
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