CN105887196A - 一种Pt3Co纳米晶体及其催化剂、制备方法和应用 - Google Patents
一种Pt3Co纳米晶体及其催化剂、制备方法和应用 Download PDFInfo
- Publication number
- CN105887196A CN105887196A CN201610241005.2A CN201610241005A CN105887196A CN 105887196 A CN105887196 A CN 105887196A CN 201610241005 A CN201610241005 A CN 201610241005A CN 105887196 A CN105887196 A CN 105887196A
- Authority
- CN
- China
- Prior art keywords
- nanocrystal
- catalyst
- pt3co
- centrifugal
- metal nano
- 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
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 75
- 238000005406 washing Methods 0.000 claims description 27
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- -1 octadecylenes Chemical class 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 235000013495 cobalt Nutrition 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000012454 non-polar solvent Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 abstract 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 22
- 230000005540 biological transmission Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002129 infrared reflectance spectroscopy Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
-
- 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种Pt3Co纳米晶体,具有八足体结构。本发明还公开了上述Pt3Co纳米晶体的制备方法,通过将乙酰丙酮铂和乙酰丙酮钴溶解于十八烯和十八烯胺的混合溶液中,再注入辛硫醇后加热搅拌得到。本发明还公开了由上述Pt3Co纳米晶体得到的Pt3Co金属纳米催化剂。本发明还公开了上述Pt3Co金属纳米催化剂的制备方法,将Pt3Co纳米晶体加入到炭黑正己烷悬浊液中,混合,清洗,干燥得到。本发明还公开了上述Pt3Co金属纳米催化剂在催化CO2加氢反应中的应用。本发明所得催化剂基于针尖效应和双金属的协同效应,导致Pt3Co纳米晶体顶点处Pt原子上电荷富集,从而大幅提升CO2加氢催化活性。
Description
技术领域
本发明涉及催化剂技术领域,尤其涉及一种Pt3Co纳米晶体及其制备方法,还涉及一种Pt3Co金属纳米催化剂及其制备、应用。
背景技术
CO2还原固定生成化工产品在能源可持续发展和环境友好型能源需求上有着重要意义。随着工业的发展,化石燃料的需求量日益增长,随之燃烧产生大量的CO2排放,成为近年来全球气候变暖的主要原因之一。同时考虑到化石燃料储量的有限性,太阳能、风能、氢能源等在运输和储存上的限制性,CO2的捕获和固定则有着重要意义。CO2还原固定后的产物甲醇,作为一种重要的有机原料,可以用于制备甲醛、二甲醚、乙酸、甲基叔丁醚等重要化工产品,同时甲醇也可以直接作为燃料使用。另外由甲醇脱水生成的二甲醚,是一种很容易液化的燃料,类似于液化石油气,由于其高十六烷值和几乎无烟排放,可以作为柴油的替代品。甲醇还可以转化为烯烃,合成高分子产业中重要的原料如乙烯、丙烯。
CO2分子作为一种极其稳定的分子,有着116.3pm的键长和1072kJ/mol的键离解能,其活化是CO2还原反应中一个非常重要的步骤。通过使用异相催化剂可以大幅地促进该过程的进行,目前用于CO2还原的异相催化剂主要包括Pt、Au、Ru、Cu以及其合金。已有的研究如Cu和ZnO/CdSe的异质结,通过提升Cu的负电荷密度,促进了CO2活化,从而加速反应的进行,又如在Cu/CeO2界面上,可以催化活化CO2到CO2 δ -,同样对反应有着促进作用。
发明内容
本发明的目的是提供一种具有八足体结构的Pt3Co纳米晶体,以及由其制备的Pt3Co金属纳米催化剂,能结合针尖效应和双金属的协同效应,使得Pt3Co纳米晶体顶点处Pt原子上电荷富集,并最终提高其催化活性;通过合成八足体结构的Pt3Co纳米晶体,将更好的发挥其在CO2加氢反应中的催化优势并发掘出更广阔的应用潜能。
本发明提出的一种Pt3Co纳米晶体,具有八足体结构,所述八足体结构为具有八根枝杈的星型结构。
优选地,所述八足体结构的平均粒径为10~15nm,优选为13nm。
优选地,每根所述枝杈的长度为5~10nm,厚度为2~4nm。
优选地,每根所述枝杈的长度为8nm,厚度为3nm。
通过扫描透射电子显微镜可发明,本发明的Pt3Co纳米晶体中Pt原子和Co原子均匀分布在八足体结构中,再通过电感耦合等离子体原子发射光谱法测定Pt和Co的摩尔比为19:6。
本发明还提出的上述Pt3Co纳米晶体的制备方法,包括如下步骤:按重量份将27份乙酰丙酮钴、30份乙酰丙酮铂、十八烯和十八烯胺混合得到混合液A,其中乙酰丙酮钴和十八烯的重量体积比(g/L)为27:4,十八烯和十八烯胺的体积比为4:5;向混合液A中加入10份辛硫醇混合均匀得到混合液B;将混合液B置入油浴锅中加热30~35min,油浴锅的温度为170~175℃,然后进行清洗得到Pt3Co纳米晶体。
优选地,清洗的具体操作如下:将油浴加热后的混合物料进行离心,将离心所得产物用非极性溶剂进行超声洗涤,然后重复上述离心、超声洗涤步骤,最后离心收集。
优选地,离心转速均为13000~14000转/min,离心的时间均为5~7min。
优选地,超声洗涤时间为1~2min。
优选地,非极性溶剂为正己烷。
本发明还提出的一种Pt3Co金属纳米催化剂,为炭黑表面负载有上述Pt3Co纳米晶体。
优选地,炭黑与上述Pt3Co纳米晶体的重量比为47~48:2~3。
本发明还提出的上述Pt3Co金属纳米催化剂的制备方法,包括如下步骤:将上述Pt3Co纳米晶体重新分散在非极性溶剂中,再加入到炭黑正己烷悬浊液中,混合,清洗,干燥后得到Pt3Co金属纳米催化剂。
优选地,炭黑正己烷悬浊液的浓度为0.32~0.36mg/mL。
优选地,混合的具体操作为:进行超声处理3~4h,接着进行搅拌12~14h。
优选地,清洗的具体操作如下:将混合后的物料进行离心,然后将离心所得产物进行超声洗涤,然后重复离心、超声洗涤步骤。
优选地,将混合后的物料进行离心,然后将离心所得产物用正己烷进行超声洗涤,接着离心收集,再用乙醇进行超声洗涤,然后离心收集,继续用乙醇进行超声洗涤,接着离心收集,再用水进行超声洗涤,然后离心收集,继续用水进行超声洗涤,最后离心收集。
优选地,离心转速均为45000~50000转/min,离心的时间均为4~6min。
优选地,干燥温度为70~72℃,干燥时间为2~3h。
本发明还提出的上述Pt3Co金属纳米催化剂在催化CO2加氢反应中的应用。
异相催化剂表面的电子结构是影响催化剂性能的主要因素,一方面可以通过调节异相催化剂表面结构来改变其电子分布,理论计算表明电子更倾向于富集在形状尖锐的区域,例如顶点和边缘;另一方面,由于合金中电负性的差异导致的两种金属间的电荷转移,从而电荷会富集在电负性较高的原子上并作为 活性中心,促进反应的进行。
本发明的Pt3Co纳米晶体具有八足体结构,结合上述的针尖效应和双金属的协同效应,使得Pt3Co纳米晶体顶点处Pt原子上电荷富集,由其制备的得到的Pt3Co金属纳米催化剂在CO2加氢催化反应中展示出了很高的催化活性,相比于已有的Pt3Co立方体、Pt八足体、Pt立方体纳米晶体催化剂,其转化效率分别是它们的2.2倍、6.1倍和6.6倍,同时可以通过红外反射吸收光谱观测到在Pt3Co金属纳米催化剂作用下CO2到CO2 δ -的转变。
附图说明
图1为本发明实施1所得Pt3Co纳米晶体的透射电子显微镜图。
图2为本发明实施1所得Pt3Co纳米晶体的扫描透射电子显微镜高角环形暗场像。
图3为本发明实施1所得单个Pt3Co纳米晶体颗粒的扫描透射电子显微镜高角环形暗场像。
图4为本发明实施1所得单个Pt3Co纳米晶体颗粒的扫描透射电子显微镜元素分布分析图。
图5为本发明实施1所得单个Pt3Co纳米晶体颗粒的元素线扫描图。
图6为本发明实施1所得单个Pt3Co纳米晶体颗粒在不同取向的扫描透射电子显微镜-傅里叶变换图;其中A1为单个Pt3Co纳米晶体颗粒在[111]取向上的扫描透射电子显微镜高角环形暗场像,A2为A1的傅里叶变换图,B1为单个Pt3Co纳米晶体颗粒在[100]取向上的扫描透射电子显微镜高角环形暗场像,B2为B1的傅里叶变换图,C1为单个Pt3Co纳米晶体颗粒在[110]取向上的扫描透射电子显微镜高角环形暗场像,C2为C1的傅里叶变换图。
图7为本发明实施例2所得Pt3Co金属纳米催化剂在CO2加氢催化反应中 甲醇产量-时间折线图。
图8为本发明实施例2所得Pt3Co金属纳米催化剂对CO2加氢反应进行数次催化后甲醇总产量的变化图。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提供的一种具有八足体Pt3Co纳米晶体的制备方法,包括如下步骤:
在常温下,依次向20mL的玻璃反应瓶中加入:27mg乙酰丙酮钴、30mg乙酰丙酮铂、4ml十八烯和5ml十八烯胺,随后注入10mg辛硫醇,将该混合液摇晃均匀,置入170℃的油浴锅中加热30min,将油浴加热后的混合物料进行离心,离心的转速为13000转/分钟,离心的时间为5min,将离心所得产物用正己烷进行超声洗涤1min,然后重复上述离心、超声洗涤步骤两次,最后离心收集得到Pt3Co纳米晶体。
对所得Pt3Co纳米晶体进行电镜透射和扫描,如图1-4和图6所示。参照图图1-4和图6,实施例1所得Pt3Co纳米晶体具有八足体结构,即为具有八根枝杈的星型结构,其晶体的平均粒径为13nm,其中枝杈的平均长度为8nm,平均厚度为3nm。
实施例2
本发明提供的一种Pt3Co金属纳米催化剂的制备方法,包括如下步骤:将实施例1所得Pt3Co纳米晶体重新分散在正己烷中得到浓度为1mg/mL的Pt3Co纳米晶体溶液;将340μL浓度为1mg/mL的Pt3Co纳米晶体溶液中注入到20mL浓度为0.34mg/mL的炭黑正己烷溶液混合后,超声处理3h,接着进行搅拌12h,再进行离心后,然后将离心所得产物用正己烷进行超声洗涤1min,接着离心收 集,再用乙醇进行超声洗涤1min,然后离心收集,继续用乙醇进行超声洗涤1min,接着离心收集,再用水进行超声洗涤1min,然后离心收集,继续用水进行超声洗涤1min,然后离心收集,接着在70℃烘干2h得到Pt3Co金属纳米催化剂。
上述离心转速为45000转/分钟,离心的时间为5min。
经检测,所得Pt3Co金属纳米催化剂中铂钴质量分数为5%。
实施例3
将20mg实施例2所得Pt3Co金属纳米催化剂加入到100ml高压反应釜中,再加入30ml H2O,接着充入800KPa CO2气体和2400KPa H2气体,升温至150℃后,保温反应5h,保温反应过程中维持300转/分钟的转速。
Pt3Co金属纳米催化剂催化CO2加氢反应中,甲醇产量-时间折线图如图7所示。同时该催化剂对CO2加氢反应进行数次催化后甲醇总产量的变化图如图8所示。参照图7和图8,本发明所得Pt3Co金属纳米催化剂在加氢反应中催化效果好,转化效率高,而且其催化活性在多次反应后仍保持有很高的反应活性,其催化转化率并未有大幅度的降低,为催化剂的回收重复利用提供了可能。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种Pt3Co纳米晶体,其特征在于,所述Pt3Co纳米晶体具有八足体结构,所述八足体结构为具有八根枝杈的星型结构。
2.根据权利要求1所述Pt3Co纳米晶体,其特征在于,所述八足体结构的平均粒径为10~15nm。
3.根据权利要求1或2所述Pt3Co纳米晶体,其特征在于,每根所述枝杈的长度为5~10nm,厚度为2~4nm。
4.一种如权利要求1-3任一项所述Pt3Co纳米晶体的制备方法,其特征在于,包括如下步骤:按重量份将27份乙酰丙酮钴、30份乙酰丙酮铂、十八烯和十八烯胺混合得到混合液A,其中乙酰丙酮钴和十八烯的重量体积比(g/L)为27:4,十八烯和十八烯胺的体积比为4:5;向混合液A中加入10份辛硫醇混合均匀得到混合液B;将混合液B置入油浴锅中加热30~35min,油浴锅的温度为170~175℃,然后进行清洗得到Pt3Co纳米晶体。
5.根据权利要求4所述Pt3Co纳米晶体的制备方法,其特征在于,清洗的具体操作如下:将油浴加热后的混合物料进行离心,将离心所得产物用非极性溶剂进行超声洗涤,然后重复上述离心、超声洗涤步骤,最后离心收集;优选地,离心转速均为13000~14000转/min,离心的时间均为5~7min;优选地,超声洗涤时间为1~2min;优选地,非极性溶剂为正己烷。
6.一种Pt3Co金属纳米催化剂,其特征在于,所述催化剂为炭黑表面负载有如权利要求1-3任一项所述Pt3Co纳米晶体。
7.根据权利要求6所述Pt3Co金属纳米催化剂,其特征在于,炭黑与如权利要求1-3任一项所述Pt3Co纳米晶体的重量比为47~48:2~3。
8.一种如权利要求6或7所述Pt3Co金属纳米催化剂的制备方法,其特征在于,包括如下步骤:将如权利要求1-3任一项所述Pt3Co纳米晶体重新分散在非极性溶剂中,再加入到炭黑正己烷悬浊液中,混合,清洗,干燥后得到Pt3Co金属纳米催化剂。
9.根据权利要求8所述Pt3Co金属纳米催化剂的制备方法,其特征在于,炭黑正己烷悬浊液的浓度为0.32~0.36mg/mL;优选地,混合的具体操作为:进行超声处理3~4h,接着进行搅拌12~14h;
优选地,清洗的具体操作如下:将混合后的物料进行离心,然后将离心所得产物进行超声洗涤,然后重复离心、超声洗涤步骤;优选地,将混合后的物料进行离心,然后将离心所得产物用正己烷进行超声洗涤,接着离心收集,再用乙醇进行超声洗涤,然后离心收集,继续用乙醇进行超声洗涤,接着离心收集,再用水进行超声洗涤,然后离心收集,继续用水进行超声洗涤,最后离心收集;优选地,离心转速均为45000~50000转/min,离心的时间均为4~6min;优选地,干燥温度为70~72℃,干燥时间为2~3h。
10.一种如权利要求6或7所述Pt3Co金属纳米催化剂在催化CO2加氢反应中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610241005.2A CN105887196B (zh) | 2016-04-15 | 2016-04-15 | 一种Pt3Co纳米晶体及其催化剂、制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610241005.2A CN105887196B (zh) | 2016-04-15 | 2016-04-15 | 一种Pt3Co纳米晶体及其催化剂、制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105887196A true CN105887196A (zh) | 2016-08-24 |
CN105887196B CN105887196B (zh) | 2018-10-12 |
Family
ID=56705068
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610241005.2A Active CN105887196B (zh) | 2016-04-15 | 2016-04-15 | 一种Pt3Co纳米晶体及其催化剂、制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105887196B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112820888A (zh) * | 2021-03-19 | 2021-05-18 | 中国科学技术大学 | 单原子与纳米晶复合结构的燃料电池催化剂的制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102059126A (zh) * | 2009-11-18 | 2011-05-18 | 现代自动车株式会社 | PtCo纳米立方体催化剂的制备方法 |
US20110124499A1 (en) * | 2009-11-23 | 2011-05-26 | The Research Foundation Of State University Of New York | CATALYTIC PLATINUM AND ITS 3d-TRANSITION-METAL ALLOY NANOPARTICLES |
US20110124500A1 (en) * | 2009-11-23 | 2011-05-26 | The Research Foundation Of State University Of New York | Catalytic platinum-copper alloy nanoparticles |
CN102728384A (zh) * | 2011-04-12 | 2012-10-17 | 通用汽车环球科技运作有限责任公司 | 铂-合金纳米粒子的合成和包含其的负载型催化剂 |
CN103111308A (zh) * | 2013-03-05 | 2013-05-22 | 北京大学 | 水相直接合成Pt-Co双金属纳米粒子的方法及应用 |
CN103352254A (zh) * | 2013-07-05 | 2013-10-16 | 浙江大学 | 一种八面体铂铜合金纳米晶的制备方法及其制备的八面体铂铜合金纳米晶 |
CN105251509A (zh) * | 2015-11-26 | 2016-01-20 | 河北工业大学 | 一种Pt-Co花状纳米催化剂的制备方法 |
CN105413709A (zh) * | 2015-12-11 | 2016-03-23 | 中国科学院上海高等研究院 | 一种多立方枝状结构的铂钴纳米双金属催化剂及其制备方法和应用 |
-
2016
- 2016-04-15 CN CN201610241005.2A patent/CN105887196B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102059126A (zh) * | 2009-11-18 | 2011-05-18 | 现代自动车株式会社 | PtCo纳米立方体催化剂的制备方法 |
US20110124499A1 (en) * | 2009-11-23 | 2011-05-26 | The Research Foundation Of State University Of New York | CATALYTIC PLATINUM AND ITS 3d-TRANSITION-METAL ALLOY NANOPARTICLES |
US20110124500A1 (en) * | 2009-11-23 | 2011-05-26 | The Research Foundation Of State University Of New York | Catalytic platinum-copper alloy nanoparticles |
CN102728384A (zh) * | 2011-04-12 | 2012-10-17 | 通用汽车环球科技运作有限责任公司 | 铂-合金纳米粒子的合成和包含其的负载型催化剂 |
CN103111308A (zh) * | 2013-03-05 | 2013-05-22 | 北京大学 | 水相直接合成Pt-Co双金属纳米粒子的方法及应用 |
CN103352254A (zh) * | 2013-07-05 | 2013-10-16 | 浙江大学 | 一种八面体铂铜合金纳米晶的制备方法及其制备的八面体铂铜合金纳米晶 |
CN105251509A (zh) * | 2015-11-26 | 2016-01-20 | 河北工业大学 | 一种Pt-Co花状纳米催化剂的制备方法 |
CN105413709A (zh) * | 2015-12-11 | 2016-03-23 | 中国科学院上海高等研究院 | 一种多立方枝状结构的铂钴纳米双金属催化剂及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
BRIAN PATRICK ET AL.: ""Atomic Structure and Composition of "Pt3Co" Nanocatalysts in Fuel Cells: An Aberration-Corrected STEM HAADF Study"", 《CHEMISTRY OF MATERIALS》 * |
CHAO WANG ET AL.: "Monodisperse Pt3Co nanoparticles as electrocatalyst:the effects of particle size and pretreatment on electrocatalytic reduction of oxygen", 《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112820888A (zh) * | 2021-03-19 | 2021-05-18 | 中国科学技术大学 | 单原子与纳米晶复合结构的燃料电池催化剂的制备方法 |
CN112820888B (zh) * | 2021-03-19 | 2022-04-19 | 中国科学技术大学 | 单原子与纳米晶复合结构的燃料电池催化剂的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN105887196B (zh) | 2018-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Perumal et al. | Experimental analysis of engine performance, combustion and emission using pongamia biodiesel as fuel in CI engine | |
Mansir et al. | Modified waste egg shell derived bifunctional catalyst for biodiesel production from high FFA waste cooking oil. A review | |
Changmai et al. | Biodiesel production using a renewable mesoporous solid catalyst | |
Chidambaranathan et al. | The production of biodiesel from castor oil as a potential feedstock and its usage in compression ignition Engine: A comprehensive review | |
Baskar et al. | Optimization and kinetics of biodiesel production from Mahua oil using manganese doped zinc oxide nanocatalyst | |
Basumatary et al. | Application of agro-waste derived materials as heterogeneous base catalysts for biodiesel synthesis | |
Muthu et al. | Synthesis of biodiesel from Neem oil using sulfated zirconia via tranesterification | |
Keskin et al. | Biodiesel production from tall oil with synthesized Mn and Ni based additives: effects of the additives on fuel consumption and emissions | |
Duz et al. | Alkali catalyzed transesterification of safflower seed oil assisted by microwave irradiation | |
Singh et al. | Optimization of biodiesel synthesis from microalgal (Spirulina platensis) oil by using a novel heterogeneous catalyst, β-strontium silicate (β-Sr2SiO4) | |
Lian et al. | Integration of extraction and transesterification of lipid from jatropha seeds for the production of biodiesel | |
Kamran et al. | Biodiesel production from Elaeagnus angustifolia. L seed as a novel waste feedstock using potassium hydroxide catalyst | |
Orugba et al. | Production of biodiesel from a novel combination of raphia africana kernel oil and turtle shell (Centrochelys Sulcata) Heterogenous Catalyst | |
Jamil et al. | Waste Balanites aegyptiaca seed oil as a potential source for biodiesel production in the presence of a novel mixed metallic oxide catalyst | |
Ismail et al. | Biodiesel production from castor oil and its application in diesel engine | |
Hidayat et al. | Esterification free fatty acid in sludge palm oil using ZrO2/SO42−–rice husk ash catalyst | |
Komintarachat et al. | Catalytic enhancement of calcium oxide from green mussel shell by potassium chloride impregnation for waste cooking oil-based biodiesel production | |
Rashid et al. | Comparative study of the methanolysis and ethanolysis of Maize oil using alkaline catalysts | |
CN105887196A (zh) | 一种Pt3Co纳米晶体及其催化剂、制备方法和应用 | |
Arun et al. | Upgradation of Nostoc punctriforme under subcritical conditions into liquid hydrocarbons (bio-oil) via hydro-deoxygenation: Optimization and engine tests | |
Osagiede et al. | Biochar-based bi-functional catalyst derived from rubber seed shell and eggshell for biodiesel production from waste cooking oil | |
Benitha et al. | Enhanced yield of biodiesel through nano catalytic transesterification of palm oil | |
Subramani et al. | Production of Garcinia gummi-gutta methyl ester (GGME) as a potential alternative feedstock for existing unmodified DI diesel engine: combustion, performance and emission characteristics | |
CN102417824A (zh) | 一种烃类燃料的制备方法 | |
CN101590405B (zh) | 用于脂肪酸酯制备烷烃的催化剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |