CN106563483A - 一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法 - Google Patents
一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法 Download PDFInfo
- Publication number
- CN106563483A CN106563483A CN201610953699.2A CN201610953699A CN106563483A CN 106563483 A CN106563483 A CN 106563483A CN 201610953699 A CN201610953699 A CN 201610953699A CN 106563483 A CN106563483 A CN 106563483A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- coated copper
- product
- layer
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000004005 microsphere Substances 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 230000000802 nitrating effect Effects 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000011805 ball Substances 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011806 microball Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract 4
- 229920000877 Melamine resin Polymers 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000003763 carbonization Methods 0.000 abstract 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 241000143432 Daldinia concentrica Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IPMQSLPLJDKUPI-UHFFFAOYSA-N 2-oxocyclopentane-1-carbonitrile Chemical compound O=C1CCCC1C#N IPMQSLPLJDKUPI-UHFFFAOYSA-N 0.000 description 1
- RNMCQEMQGJHTQF-UHFFFAOYSA-N 3,5,6,7-tetrahydrotetrazolo[1,5-b][1,2,4]triazine Chemical compound N1CCN=C2N=NNN21 RNMCQEMQGJHTQF-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical class NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及铜基催化剂的制备领域，具体是一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法，包括如下步骤：⑴在每粒SiO2微球表面包裹一层酚醛树脂；⑵将步骤⑴的产物进行三聚氰胺以及铜盐溶液的过量浸渍；⑶在步骤⑵的产物表面进行SiO2微球的再包裹，然后最外层再包裹一层酚醛树脂；⑷将步骤⑶的产物进行高温碳化处理，两层酚醛树脂被碳化；采用HF洗涤处理，SiO2微球被去除；然后将产物在氢气氛围下活化处理，获得催化剂。催化活性高达1670 mg/g∙h，相比较于结构简易的碳包铜催化剂，有效地提高了催化活性及稳定性，反应后活性组分不易团聚，是一种先进的制备掺氮中空碳球包覆纳米铜催化剂的方法。
Description
技术领域
本发明涉及铜基催化剂的制备领域，具体是一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法，可用于催化甲醇氧化羰基化制备碳酸二甲酯。
背景技术
近年来，人们已将纳米尺寸上的限域效应成功应用于催化科学。碳材料具有稳定的化学性质、低质量密度、优良的导电性，而常被广泛地用于催化领域。目前，在限域效应基础上，碳纳米管、石墨烯、中空碳球等碳材料常被设计为催化剂载体。
铜基催化剂催化甲醇氧化羰基化合成碳酸二甲酯(DMC)的反应，因其生产成本低、对设备腐蚀性小、选择性高、原料廉价易得等优点，而得到很广泛的应用。专利CN201410638225.X报道了一种核壳型碳包覆纳米铜催化剂的制备方法，此方法制得的催化剂稳定性高，但活性组分在壳层内部发生团聚而使得催化活性不理想。相关文献报道中，将碳壳进行杂原子掺杂可有效改善其物理、化学性能，例如在碳层中进行氮掺杂，氮原子提供的孤对电子可改变碳材料的局部电荷分布，增强载体与金属之间的作用力，显著地提高了金属颗粒在碳材料表面的分散度。另外研究中也发现多层核壳结构也可有效避免活性组分的团聚。
针对甲醇氧化羰基化制备DMC中活性组分易团聚的问题，制备双层结构的掺氮碳球是解决这一难题的新方法，目前仍处于研究之中。
发明内容
为了优化核壳结构在甲醇氧化羰基化制DMC中的催化性能，本发明提供了一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法。
本发明是通过以下技术方案实现的：一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法，包括如下步骤：
⑴在每粒SiO2微球表面包裹一层酚醛树脂；
⑵将步骤⑴的产物进行三聚氰胺以及铜盐溶液的过量浸渍；
⑶在步骤⑵的产物表面进行SiO2微球的再包裹，然后最外层再包裹一层酚醛树脂；
⑷将步骤⑶的产物进行高温碳化处理，两层酚醛树脂被碳化；采用HF洗涤处理，SiO2微球被去除；然后将产物在氢气氛围下活化处理，获得催化剂。
本发明的核壳结构利用中空壳层的屏障作用可使得内核组分免受外界环境因素的影响。利用特殊的限域结构体系，可有效防止金属纳米核在反应中的聚集、长大，最大程度的保证了金属纳米粒子的组成和结构的完整性。其次，通过原位合成法进行掺氮，有效的将氮元素引入碳骨架，在反应过程中可充分发挥氮元素的化学作用，增加催化剂的稳定性。因此，本发明所述催化剂无论在结构上还是性能上都能够解决活性组分易团聚的问题。
具体实施时，步骤⑶的产物惰性气体氛围下，碳化温度700℃±5℃，保温5h。
优选的，所述在氢气氛围下活化处理为：在氢气氛围下，活化温度400℃±5℃，保温2h。
本发明与背景技术相比之下具有明显的先进性，双碳层结构提供了优良的空间限域效应，有效避免活性组分在反应过程中的增长团聚，同时构筑了高活性的纳米反应器。其所制备的催化剂对于避免活性组分的团聚和剥离具有显著地效果。实验数据精确翔实，成本低，原料易得，产物为黑色粉体，粉体颗粒直径不大于500nm，产物纯度达98.7%，催化活性高达1670mg/g∙h，相比较于结构简易的碳包铜催化剂，有效地提高了催化活性及稳定性，反应后活性组分不易团聚，是一种先进的制备掺氮中空碳球包覆纳米铜催化剂的方法。
附图说明
图1为本发明所述双层中空掺氮碳球包覆铜纳米催化剂的制备工艺流程图。
图2为本发明所述双层中空掺氮碳球包覆铜纳米催化剂的形貌图。由图3可以看出，制备得到的催化剂是核壳型粉体，形貌规整，大小均一。
图3为本发明所述双层中空掺氮碳球包覆铜纳米催化剂的射线衍射图谱。图中：纵坐标为衍射强度，横坐标为衍射角2θ，图中43.31º、50.43º、74.13º为零价铜的衍射峰，36.42º、61.34º为一价亚铜的衍射峰。由图可得出结论，衍射峰峰型尖锐，可表明单质铜结晶度高。
具体实施方式
本发明使用的化学物质材料为：无水乙醇、去离子水、氨水、正硅酸乙酯（TEOS）、3-氨基酚、甲醛、三聚氰胺、硝酸铜、甲醇、十六烷基三甲基溴化铵（CTAB）、氢氟酸（40%）、高纯氮气、高纯氢气，其准备用量如下：以克、毫升、厘米3为计量单位
无水乙醇:CH3CH2OH 液体100ml±0.1ml
去离子水:H2O 液体3000ml±50ml
氨水:NH3•H2O 液体6ml±0.1ml
甲醇:CH3OH 液体40ml±0.1ml
正硅酸乙酯:C4H12O4Si 液体6ml±0.1ml
甲醛：HCHO 液体0.61ml±0.01ml
正己醇：C6H14O 液体30ml±0.1ml
氢氟酸：HF 液体300ml±10ml
十六烷基三甲基溴化铵:C19H42BrN 固体5g±0.001g
三聚氰胺:C3H6N6 固体1.0g±0.001g
3-氨基酚:C6H7NO 固体0.4g±0.001g
硝酸铜：Cu(NO3)2•3H2O 固体5g±0.001g
氢气：H2 气体100000cm3±100cm3
氮气：N2 气体100000cm3±100cm3
双层中空掺氮碳球包覆铜纳米催化剂的制备方法如下：
(1)用Stöber法制备单分散SiO2微球：量取70ml±0.1ml无水乙醇、10ml±0.1ml去离子水、3ml±0.1ml氨水、2.5ml±0.1mlTEOS于150ml烧杯中，室温搅拌15~20min。
(2)称取0.4g±0.001g3-氨基酚同时量取0.56ml±0.1ml甲醛加入上述混合溶液中，室温持续搅拌24h，离心后用去离子水及无水乙醇各洗涤3遍，置于50℃烘箱中干燥，得到SiO2@Polymer。
(3)将(2)中干燥产物与1.0g±0.001g三聚氰胺、硝酸铜5g±0.001g分散于40ml±0.1ml甲醇溶液中，50℃持续搅拌蒸干。将产物收集后置于烧杯，量取30ml±0.1ml正己醇，放于35℃水浴中，放入5g±0.001gCTAB后剧烈搅拌5min。接着，量取3ml±0.1ml TEOS、3ml±0.1ml氨水加入上述溶液中，持续搅拌20min。
(4)称取0.4g±0.001g3-氨基酚同时量取0.56ml±0.1ml甲醛加入(3)中混合溶液，室温搅拌24h，离心、洗涤、干燥得产物一。
(5)将产物一置于管式炉中，通入的氮气流速为100cm3/min，以5℃/min升至700ºC±5℃，后在此温度下保持5h，得高温碳化后所得的产物二。
(6)产物二经20%HF溶液洗涤，得双层中空结构的催化剂。
(7)在管式炉通入氮气、氢气，氮气流速设为100cm3/min、氢气10cm3/min对催化剂进行活化。升温速率为3℃/min，活化温度为400℃±5℃，保温2h，得双层中空掺氮碳球包覆铜纳米催化剂。
(8)研磨、过筛
将活化后的催化剂用玛瑙研钵研磨，后用650目筛网过筛。
(9)产物储存
将制备的催化剂储存于氮气气氛下的样品袋中，干燥密闭储存。
(10)活性评价
催化剂活性评价在25ml容积的微型高压反应釜中进行。称取0.1g催化剂加入反应釜釜体内，加入10mL甲醇，密闭釜体后，通入反应气CO至压力为2.0MPa、O2至总压力为3.0MPa。设置搅拌速率为900 r/min，温度为110℃下反应90min后停止加热，降至室温，离心后取上层清液，再用气象色谱进行产物分析。
(11)检测、分析、表征
对制备的催化剂进行表面形貌、化学物理性能进行检测、分析和表征；
用扫描电子显微镜SEM观察样品表面形貌；
用X-射线粉末衍射仪进行晶相分析；
结论：双层掺氮中空碳球包覆铜纳米催化剂为黑色粉体，粉体颗粒直径不大于500nm，产物纯度达98.7%，催化活性高达1670 mg/g∙h，选择性高达99.99%。
Claims (3)
1.一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法，其特征在于，包括如下步骤：
⑴在每粒SiO2微球表面包裹一层酚醛树脂；
⑵将步骤⑴的产物进行三聚氰胺以及铜盐溶液的过量浸渍；
⑶在步骤⑵的产物表面进行SiO2微球的再包裹，然后最外层再包裹一层酚醛树脂；
⑷将步骤⑶的产物进行高温碳化处理，两层酚醛树脂被碳化；采用HF洗涤处理，SiO2微球被去除；然后将产物在氢气氛围下活化处理，获得催化剂。
2.根据权利要求1所述的一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法，其特征在于，所述高温碳化处理为：步骤⑶的产物惰性气体氛围下，碳化温度700℃±5℃，保温5h。
3.根据权利要求1所述的一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法，其特征在于，所述在氢气氛围下活化处理为：在氢气氛围下，活化温度400℃±5℃，保温2h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610953699.2A CN106563483B (zh) | 2016-11-03 | 2016-11-03 | 一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610953699.2A CN106563483B (zh) | 2016-11-03 | 2016-11-03 | 一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106563483A true CN106563483A (zh) | 2017-04-19 |
| CN106563483B CN106563483B (zh) | 2019-01-25 |
Family
ID=58535273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610953699.2A Active CN106563483B (zh) | 2016-11-03 | 2016-11-03 | 一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106563483B (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589922A (zh) * | 2019-01-14 | 2019-04-09 | 太原理工大学 | 一种具有高吸附性能的磁性中空碳纳米球的制备方法 |
| CN110898847A (zh) * | 2019-08-14 | 2020-03-24 | 新奥科技发展有限公司 | 一种合成气制低碳醇用复合载体型催化剂及其制备方法 |
| CN113649004A (zh) * | 2021-07-07 | 2021-11-16 | 中国科学院合肥物质科学研究院 | 一种空心碳球负载金属颗粒催化剂及其制备方法和用途 |
| CN115779954A (zh) * | 2022-12-21 | 2023-03-14 | 北京化工大学 | 一种双层核壳结构的金属单原子氮碳材料及其制备方法和用途 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR102013031741A2 (pt) * | 2013-12-10 | 2015-09-29 | Univ Estadual De Maringá | carvão ativado dopado com nitrogênio produzido a partir da regeneração térmica do material saturado com azul de metileno e sua aplicação como eletrodo para supercapacitores |
| CN105692590A (zh) * | 2016-03-17 | 2016-06-22 | 南京理工大学 | 一种氮掺杂中空介孔核壳碳球的制备方法 |
| CN106006549A (zh) * | 2016-06-30 | 2016-10-12 | 上海电力学院 | 杂原子掺杂中空碳球材料负载贵金属纳米粒子及其制备 |
| CN106058276A (zh) * | 2016-07-11 | 2016-10-26 | 华南理工大学 | 一种二氧化硅修饰的多球腔碳材料的制法及其在燃料电池膜电极中的应用 |
-
2016
- 2016-11-03 CN CN201610953699.2A patent/CN106563483B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR102013031741A2 (pt) * | 2013-12-10 | 2015-09-29 | Univ Estadual De Maringá | carvão ativado dopado com nitrogênio produzido a partir da regeneração térmica do material saturado com azul de metileno e sua aplicação como eletrodo para supercapacitores |
| CN105692590A (zh) * | 2016-03-17 | 2016-06-22 | 南京理工大学 | 一种氮掺杂中空介孔核壳碳球的制备方法 |
| CN106006549A (zh) * | 2016-06-30 | 2016-10-12 | 上海电力学院 | 杂原子掺杂中空碳球材料负载贵金属纳米粒子及其制备 |
| CN106058276A (zh) * | 2016-07-11 | 2016-10-26 | 华南理工大学 | 一种二氧化硅修饰的多球腔碳材料的制法及其在燃料电池膜电极中的应用 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589922A (zh) * | 2019-01-14 | 2019-04-09 | 太原理工大学 | 一种具有高吸附性能的磁性中空碳纳米球的制备方法 |
| CN109589922B (zh) * | 2019-01-14 | 2021-09-14 | 太原理工大学 | 一种具有高吸附性能的磁性中空碳纳米球的制备方法 |
| CN110898847A (zh) * | 2019-08-14 | 2020-03-24 | 新奥科技发展有限公司 | 一种合成气制低碳醇用复合载体型催化剂及其制备方法 |
| CN110898847B (zh) * | 2019-08-14 | 2022-05-20 | 新奥科技发展有限公司 | 一种合成气制低碳醇用复合载体型催化剂及其制备方法 |
| CN113649004A (zh) * | 2021-07-07 | 2021-11-16 | 中国科学院合肥物质科学研究院 | 一种空心碳球负载金属颗粒催化剂及其制备方法和用途 |
| CN113649004B (zh) * | 2021-07-07 | 2023-10-13 | 中国科学院合肥物质科学研究院 | 一种空心碳球负载金属颗粒催化剂及其制备方法和用途 |
| CN115779954A (zh) * | 2022-12-21 | 2023-03-14 | 北京化工大学 | 一种双层核壳结构的金属单原子氮碳材料及其制备方法和用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106563483B (zh) | 2019-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109304194B (zh) | 一种碳包覆过渡金属的纳米复合材料及应用 | |
| Vinokurov et al. | Halloysite nanotube-based cobalt mesocatalysts for hydrogen production from sodium borohydride | |
| Xiang et al. | Hydrogen generation by hydrolysis of alkaline sodium borohydride using a cobalt–zinc–boron/graphene nanocomposite treated with sodium hydroxide | |
| CN106563483A (zh) | 一种双层中空掺氮碳球包覆铜纳米催化剂的制备方法 | |
| Wang et al. | Highly active cobalt-and nitrogen-doped carbon derived from ZIF-67@ melamine towards oxygen reduction reaction | |
| Wang et al. | Highly active catalysis of methanol oxidative carbonylation over nano Cu2O supported on micropore-rich mesoporous carbon | |
| Yang et al. | Construction of core-shell mesoporous carbon nanofiber@ nickel cobaltite nanostructures as highly efficient catalysts towards 4-nitrophenol reduction | |
| Zhou et al. | Hierarchical nanoporous platinum–copper alloy nanoflowers as highly active catalysts for the hydrolytic dehydrogenation of ammonia borane | |
| Kim et al. | Ultrafine Pd nanoparticles on amine-functionalized carbon nanotubes for hydrogen production from formic acid | |
| CN111330639B (zh) | 一种多孔钴锌核壳金属有机框架化合物限域贵金属纳米粒子的杂化材料及其制备方法和应用 | |
| CN106563484B (zh) | 一种介孔型中空掺氮碳包铜纳米催化剂的制备方法 | |
| Han et al. | N-doped carbon nanoweb-supported Ni/NiO heterostructure as hybrid catalysts for hydrogen evolution reaction in an alkaline phase | |
| CN108554432A (zh) | 一种磷氮共掺杂石墨烯负载钯基催化剂及制备方法与应用 | |
| Chen et al. | The synergetic effect of h-BN shells and subsurface B in CoB x@ h-BN nanocatalysts for enhanced oxygen evolution reactions | |
| CN109603831A (zh) | 一种钴和石墨烯复合纳米材料催化剂及其制备方法 | |
| Qiu et al. | Synthesis of Fe0. 3Co0. 7/rGO nanoparticles as a high performance catalyst for the hydrolytic dehydrogenation of ammonia borane | |
| Xie et al. | Carbon supported copper catalyst prepared in situ by one-pot pyrolysis of Bougainvillea glabra: An efficient and stable catalyst for selective oxidation of cyclohexane | |
| Zhang et al. | Effect of carbon support on the catalytic performance of Cu-based nanoparticles for oxidative carbonylation of methanol | |
| Zhang et al. | MOF-derived CeO 2/Au@ SiO 2 hollow nanotubes and their catalytic activity toward 4-nitrophenol reduction | |
| Ma et al. | Clean synthesis of RGO/Mn3O4 nanocomposite with well-dispersed Pd nanoparticles as a high-performance catalyst for hydroquinone oxidation | |
| Li et al. | Enhanced adsorption and catalytic peroxymonosulfate activation by metal-free N-doped carbon hollow spheres for water depollution | |
| Liu et al. | N-rich MOFs derived N-doped carbon nanotubes encapsulating cobalt nanoparticles as efficient and magnetic recoverable catalysts for nitro aromatics reduction | |
| Xu et al. | Synthesis of multiple Ag nanoparticles loaded hollow mesoporous carbon spheres for highly efficient and recyclable catalysis | |
| Kosydar et al. | New insight into the effect of surface oxidized groups of nanostructured carbon supported Pd catalysts on the furfural hydrogenation | |
| CN109331775A (zh) | 一种绿色合成石墨烯负载纳米铁/镍复合材料及制备方法 |
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 | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Han Yahong Inventor after: Ren Jun Inventor after: Li Haixia Inventor after: Liu Shusen Inventor after: Li Zhong Inventor after: Wang Juan Inventor after: Sun Wei Inventor after: Zhu Jiyu Inventor before: Ren Jun Inventor before: Li Haixia Inventor before: Liu Shusen Inventor before: Li Zhong Inventor before: Wang Juan Inventor before: Han Yahong Inventor before: Sun Wei Inventor before: Zhu Jiyu |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |