CN110302777A - 钯纳米颗粒—活性炭复合材料及其在二氧化碳电催化还原中的应用 - Google Patents
钯纳米颗粒—活性炭复合材料及其在二氧化碳电催化还原中的应用 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 94
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 239000003610 charcoal Substances 0.000 title claims abstract description 15
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000002159 nanocrystal Substances 0.000 claims description 31
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- 239000007772 electrode material Substances 0.000 abstract 1
- 229960004424 carbon dioxide Drugs 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 9
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
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- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract
本发明公开钯纳米颗粒—活性炭复合材料及其在二氧化碳电催化还原中的应用,通过晶种生长法,通过调节前驱体浓度的用量,获得不同的钯纳米颗粒,再与活性炭进行材料复合,最后作为电极材料,在电催化二氧化碳还原中的应用。本发明制备的材料具有二氧化碳催化还原性能优越,具有一定工业价值,有效缓解当今化石燃料短缺,环境污染严重问题。
Description
技术领域
本发明涉及二氧化碳电催化阴极产一氧化碳电极领域,更加具体地说,具体为一种高指数晶面钯金属在二氧化碳电催化中的用途。
背景技术
从工业革命到现代社会,随着人类生产力的提高,对于煤、石油等传统化石能源的消耗越来越多,化石燃料的大量使用,不但造成了能源危机,同时在燃烧过程中产生大量二氧化碳。二氧化碳在大气中的含量已经从19世纪的280ppm提高到了目前的385ppm,专家预计到2100年,大气中的二氧化碳含量将达到600ppm,二氧化碳的迅速增加,会导致全球气候变暖,引发海平面上升和土地荒漠化1,2。那么利用风能、水能、太阳能等可再生能源发电来将二氧化碳转化成有价值的能源,是解决这一难题的有效方法3-5。但是由于二氧化碳本身的化学稳定性,很难被活化,导致所用的Au6,7,Ag8,Cu9,目前的转化效率不是很高。因此,寻找价格相对较低,同时活性高的金属催化剂是目前研究的热点。
金属Pd具有一定的二氧化碳电催化活性,收到广泛关注,比如Bao课题组通过制备Pd的金属颗粒10,发现当粒径在3nm左右时,催化活性很高,但是受到粒径影响很大,当粒径大时,活性急剧下降,而小粒径的钯颗粒,在反应过程中,很容易发生团聚现象,稳定性差,很难保持长时间的使用。对于研究二氧化碳的电催化的影响,还是简单停留在粒径和形貌上,没有从更深入的方面进入研究。通过合理设计催化剂,对于钯金属表面的有效调控,将大大提升催化剂CO2电催化活性,参考文献如下:
1.Zhang,L.,Zhao,Z.J.,Gong,J.,Nanostructured Materials forHeterogeneous Electrocatalytic CO2 Reduction and their Related ReactionMechanisms.Angew.Chem.Int.Ed.2017,56,11326-11353
2.Lu,Q.,Jiao,F.,Electrochemical CO2 reduction:Electrocatalyst,reaction mechanism,and process engineering.Nano Energy 2016,29,439-456.
3.Chen,Y.,Li,C.W.,Kanan,M.W.,Aqueous CO2 reduction at very lowoverpotential on oxide-derived Au nanoparticles.J.Am.Chem.Soc.2012,134,19969-19972.
4.Huang,H.,Jia,H.,Liu,Z.,Gao,P.,Zhao,J.,Luo,Z.,Yang,J.,Zeng,J.,Understanding of Strain Effects in the Electrochemical Reduction of CO2:UsingPd Nanostructures as an Ideal Platform.Angew.Chem.Int.Ed.2017,56,3594-3598.
5.Luc,W.,Collins,C.,Wang,S.,Xin,H.,He,K.,Kang,Y.,Jiao,F.,Ag-SnBimetallic Catalyst with a Core-Shell Structure for CO2Reduction.J.Am.Chem.Soc.2017,139,1885-1893.
6.Mistry,H.,Reske,R.,Zeng,Z.,Zhao,Z.J.,Greeley,J.,Strasser,P.,Cuenya,B.R.,Exceptional size-dependent activity enhancement in the electroreductionof CO2 over Au nanoparticles.J.Am.Chem.Soc.2014,136,16473-16476.
7.Zhu,W.,Zhang,Y.J.,Zhang,H.,Lv,H.,Li,Q.,Michalsky,R.,Peterson,A.A.,Sun,S.,Active and selective conversion of CO2 to CO on ultrathin Aunanowires.J.Am.Chem.Soc.2014,136,16132-16135.
8.Kim,C.,Jeon,H.S.,Eom,T.,Jee,M.S.,Kim,H.,Friend,C.M.,Min,B.K.,Hwang,Y.J.,Achieving Selective and Efficient Electrocatalytic Activity for CO2Reduction Using Immobilized Silver Nanoparticles.J.Am.Chem.Soc.2015,137,13844-13850.
9.Reske,R.,Mistry,H.,Behafarid,F.,Roldan Cuenya,B.,Strasser,P.,Particle size effects in the catalytic electroreduction of CO2 on Cunanoparticles.J.Am.Chem.Soc.2014,136,6978-6986.
10.Gao,D.,Zhou,H.,Wang,J.,Miao,S.,Yang,F.,Wang,G.,Wang,J.,Bao,X.,Size-dependent electrocatalytic reduction of CO2 over Pdnanoparticles.J.Am.Chem.Soc.2015,137,4288-4291.
发明内容
本发明的目的在于克服现有技术的不足,提供钯纳米颗粒—活性炭复合材料及其在二氧化碳电催化还原中的应用。
本发明的技术目的通过下述技术方案予以实现:
钯纳米颗粒—活性炭复合材料,由钯纳米颗粒和活性炭组成,采用活性炭加入到分散有钯纳米颗粒的体系中并超声复合。
在上述技术方案中,钯纳米颗粒和活性炭的质量比为1:(1—10),优选1:(4—8)。
在上述技术方案中,钯纳米颗粒为钯立方体纳米晶、内凹钯纳米晶或者八面体钯纳米晶,其中钯立方体纳米晶的边长为20nm—25nm;八面体钯纳米晶的边长为21nm—24nm;内凹钯纳米晶的立方体边长为22nm—26nm,Pd纳米晶在每个面上呈现一个平滑的平面凹陷结构,内凹表面与平面之间的角度为18°,对应的表面是(310)晶面。
在上述技术方案中,活性炭比表面积220—260m2/g,粒径10—30nm。
本发明的钯纳米颗粒—活性炭复合材料,以及钯纳米颗粒(钯立方体纳米晶、内凹钯纳米晶或者八面体钯纳米晶)在电催化二氧化碳还原中的应用,对于内凹钯纳米晶在-0.9V可以达到88-92%,对于钯立方体纳米晶可以达到80.5%-81.5%,对于八面体钯纳米晶可以达到67%-73%。
本发明通过晶种生长法,通过调节前驱体浓度的用量,获得不同配位数表面的催化剂,合成的催化剂颗粒表现出优秀的电催化还原二氧化碳性能。本发明的内凹钯纳米晶的{310}表面具有不饱和配位原子,对于反应过程中的中间步骤有促进作用,促进了吸附态羧基的产生,以及吸附态CO的解析,从而实现了在-0.9V的一氧化碳的法拉第效率达到90.6%。本发明中内凹钯纳米晶可通过晶种生长方法得到,操作简单,制备的材料二氧化碳催化还原性能优越,具有一定工业价值。有效缓解当今化石燃料短缺,环境污染严重问题。
附图说明
图1是本发明实施例1制备的钯立方体纳米晶的TEM照片。
图2是本发明实施例2制备的内凹Pd纳米晶催化剂颗粒的TEM照片。
图3是本发明实施例2制备的内凹Pd纳米晶催化剂颗粒的高倍TEM照片。
图4是本发明实施例3制备的八面体钯纳米晶的TEM照片。
图5是本发明实施例的性能测试曲线图(电压-电流曲线图),其中1为内凹钯纳米晶,2为钯立方体纳米晶,3为八面体钯纳米晶。
图6是本发明实施例的性能测试曲线图(电压-CO法拉第效率曲线图)。
具体实施方式
下面通过具体实施对本发明做进一步详述,以下实施例只是描述性的,不是限定性的,不能以此限定本发明的保护范围。聚乙烯吡咯烷酮(数均分子量10000)购买于上海梯希爱药品有限公司;抗坏血酸购买于国药集团,溴化钾、氯化钾、碳酸氢钾购买于天津光复药品有限公司,活性炭购买于美国卡博特公司型号VX-72颗粒状,比表面积254m2/g,粒径30nm,密度256.3g/L,超纯水用实验室超纯水机制备,氯钯酸钠购买于北京百灵威药品平有限公司,甲醛购买于阿尔法艾莎有限公司。
首先,依据参考文献进行钯立方体纳米晶、内凹钯纳米晶和八面体钯纳米晶的制备:
(1)Palladium nanocrystals enclosed by{100}and{111}facets incontrolled proportions and their catalytic activities for formic acidoxidation.Mingshang Jin,Hui Zhang,Zhaoxiong Xi and Younan Xia,EnergyEnviron.Sci.,2012,5,6352.
(2)Synthesis of Pd Nanocrystals Enclosed by{100}Facets and with Sizes<10nm for Application in CO Oxidation.Mingshang Jin1,Hongyang Liu,Hui Zhang,Zhaoxiong Xie,Jingyue Liu and Younan Xia,Nano Res.2011,4(1):83–91.
(3)Palladium Concave Nanocubes with High-Index Facets and TheirEnhanced Catalytic Properties.Mingshang Jin,Hui Zhang,Zhaoxiong Xie andYounan Xia,Angew.Chem.Int.Ed.2011,50,7850–7854.
实施例1钯立方体纳米晶的制备
将105mg聚乙烯吡咯烷酮和60mg抗坏血酸和600mg溴化钾溶解在8ml水中混合均匀,将盛有反应物的玻璃器置于80℃的水浴锅中,再加入含有57mg氯钯酸钠的3ml水溶液,在80℃下搅拌反应3小时,反应结束后,自然冷却至室温20—25摄氏度。将反应后的溶液转移到50mL离心管中,用水清洗三次,每次转速设置为9800r/min,10min。离心清洗后产物备用,如图1所示,制备的立方体钯,可以看到Pd的分散非常均匀,大小相近,立方体的边长在20nm-23nm范围内。
实施例2内凹钯纳米晶的制备
首先按照实施例1步骤进行钯立方体纳米晶的制备,将制备的钯立方体纳米晶(即钯立方体)分散在8ml的水溶液中。取其中0.3ml置于20ml玻璃瓶中,向其中加入8ml水,105mg聚乙烯吡咯烷酮,600mg溴化钾和60mg抗坏血酸,将玻璃瓶放在60度水浴中搅拌并加热,10分钟后向玻璃瓶中加入含有14.5mg的3ml氯钯酸钠水溶液。在60度下持续加热反应3小时,反应结束后,冷却至室温。将反应后的溶液转移到50mL离心管中,用水清洗三次,每次转速设置为9000r/min,10min,最后分散在1ml水中。如附图2所示,看到Pd的分散非常均匀,大小相近,立方体的边长在22nm-26nm范围内,Pd纳米晶在每个面上不是呈现一个平滑的平面凹陷结构。如附图3所示,内凹Pd纳米晶高倍电镜图,内凹的Pd纳米晶的米勒指数可以通过量取内凹表面与平面之间的角度来确定,通过量取,我们获得了这一夹角为18°,根据参考文献,18°对应的表面是(310)晶面。
首先按照实施例1步骤进行钯立方体纳米晶的制备,将制备的立方体分散在8ml的水溶液中。取其中0.3ml置于20ml玻璃瓶中,向其中加入8ml水,105mg聚乙烯吡咯烷酮,1200mg溴化钾和60mg抗坏血酸,将玻璃瓶放在60度水浴中搅拌并加热,10分钟后向玻璃瓶中加入含有14.5mg的3ml氯钯酸钠水溶液。在60度下持续加热反应3小时,反应结束后,冷却至室温。将反应后的溶液转移到50mL离心管中,用水清洗三次,每次转速设置为9000r/min,10min,最后分散在1ml水中,以制备凹陷程度不同Pd纳米晶。
实施例3八面体钯纳米晶的制备
首先按照实施例1步骤进行钯立方体纳米晶的制备,将制备的立方体分散在8ml的水溶液中。取其中0.3ml置于20ml玻璃瓶中,向其中加入8ml水,105mg聚乙烯吡咯烷酮,100ul甲醛,将玻璃瓶放在60度水浴中搅拌并加热,10分钟后向玻璃瓶中加入含有29mg的3ml氯钯酸钠水溶液。在60度下持续加热反应3小时,反应结束后,冷却至室温。将反应后的溶液转移到50mL离心管中,用水清洗三次,每次转速设置为9000r/min,10min,最后分散在1ml水中。如附图4所示,八面体的边长在21nm-24nm范围内。
利用依照依据参考文献进行钯立方体纳米晶、内凹钯纳米晶和八面体钯纳米晶,分别与活性炭共混分散,以形成钯纳米颗粒—活性炭复合材料,制备简述如下:把含金属纳米晶的水溶液和活性炭在超声机中超声3h,以实现共混分散且形成均匀分散状态,获得目标催化剂,其中钯纳米晶和活性炭的质量比为1:4。
针对利用三种不同钯纳米晶制备的复合材料的性能进行表征,用移液枪取50微升的目标催化剂滴涂在直径为8mm的玻碳电极上,静止1h,待电极干后备用,玻碳电极作为工作电极,银/氯化银电极作为参比电极,铂电极作为对电极。将电极插入到带有密封头的H型电解槽中,电解槽的容积是150ml,槽中注入100ml 0.1M碳酸氢钾水溶液,将CO2气瓶中的气体通过进气管通入电解槽中,通气30min中,此时溶液pH为6.8,此时将装置与电化学工作站相连,在一定电压下通电反应,产生的产物通过出气管导入气相色谱,气相色谱检测产物一氧化碳和氢气,参与反应面积为0.5cm2,反应时间为30分钟。评价方法:一氧化碳法拉第效率=(产生的一氧化碳摩尔量*2*96485)/通电产生的库仑量。如附图所示,在线扫过程中,可以看到随着电压的增加三种催化剂的电流密度均有增加,其中对于内凹Pd纳米晶的电流最大;对于CO法拉第效率,可以看到随着电压变负,三种催化剂都体现一个效率先增大,然后减小的过程。对于内凹Pd纳米晶在-0.9V可以达到88-92%,对于立方体Pd可以达到80.5%-81.5%,对于Pd八面体可以达到67%-73%,三者均有很好的电催化二氧化碳还原活性,其中内凹Pd纳米晶的活性最好,可以在90%以上,说明形成的配位不饱和的表面,可以提升二氧化碳电催化性能。
根据本发明内容进行调整,均可实现复合材料的制备且表现出与实施例基本一致的性能。以上对本发明做了示例性的描述,应该说明的是,在不脱离本发明的核心的情况下,任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。
Claims (10)
1.钯纳米颗粒—活性炭复合材料,其特征在于,由钯纳米颗粒和活性炭组成,采用活性炭加入到分散有钯纳米颗粒的体系中并超声复合,钯纳米颗粒和活性炭的质量比为1:(1—10)。
2.根据权利要求1所述的钯纳米颗粒—活性炭复合材料,其特征在于,钯纳米颗粒和活性炭的质量比为1:(4—8)。
3.根据权利要求1所述的钯纳米颗粒—活性炭复合材料,其特征在于,活性炭比表面积220—260m2/g,粒径10—30nm。
4.根据权利要求1所述的钯纳米颗粒—活性炭复合材料,其特征在于,钯纳米颗粒为钯立方体纳米晶、内凹钯纳米晶或者八面体钯纳米晶,其中钯立方体纳米晶的边长为20nm—25nm;八面体钯纳米晶的边长为21nm—24nm;内凹钯纳米晶的立方体边长为22nm—26nm,Pd纳米晶在每个面上呈现一个平滑的平面凹陷结构,内凹表面与平面之间的角度为18°,对应的表面是(310)晶面。
5.如权利要求1—5之一所述的钯纳米颗粒—活性炭复合材料在电催化二氧化碳还原中的应用,其特征在于,对于内凹钯纳米晶在-0.9V达到88-92%,对于钯立方体纳米晶达到80.5%-81.5%,对于八面体钯纳米晶达到67%-73%。
6.钯纳米颗粒在电催化二氧化碳还原中的应用,其特征在于,采用活性炭加入到分散有钯纳米颗粒的体系中并超声复合,钯纳米颗粒为钯立方体纳米晶、内凹钯纳米晶或者八面体钯纳米晶。
7.根据权利要求6所述的钯纳米颗粒在电催化二氧化碳还原中的应用,其特征在于,钯纳米颗粒和活性炭的质量比为1:(1—10),优选1:(4—8)。
8.根据权利要求6所述的钯纳米颗粒在电催化二氧化碳还原中的应用,其特征在于,活性炭比表面积220—260m2/g,粒径10—30nm。
9.根据权利要求6所述的钯纳米颗粒在电催化二氧化碳还原中的应用,其特征在于,钯立方体纳米晶的边长为20nm—25nm;八面体钯纳米晶的边长为21nm—24nm;内凹钯纳米晶的立方体边长为22nm—26nm,Pd纳米晶在每个面上呈现一个平滑的平面凹陷结构,内凹表面与平面之间的角度为18°,对应的表面是(310)晶面。
10.根据权利要求6所述的钯纳米颗粒在电催化二氧化碳还原中的应用,其特征在于,对于内凹钯纳米晶在-0.9V达到88-92%,对于钯立方体纳米晶达到80.5%-81.5%,对于八面体钯纳米晶达到67%-73%。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111686719A (zh) * | 2020-06-17 | 2020-09-22 | 青岛科技大学 | 一种钯金属/碳纸催化剂及其制备方法和应用 |
CN114406278A (zh) * | 2021-12-10 | 2022-04-29 | 深圳市百翱生物科技有限公司 | 一种钯纳米立方体颗粒的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030178707A1 (en) * | 2002-03-21 | 2003-09-25 | Abbott Donald C. | Preplated stamped small outline no-lead leadframes having etched profiles |
CN102764648A (zh) * | 2011-05-06 | 2012-11-07 | 北京林业大学 | 一种钯催化剂的制备方法,由该方法制备的钯催化剂及应用 |
US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
WO2015108608A2 (en) * | 2013-11-04 | 2015-07-23 | Portland State University | Method of making a metallic composite and use thereof |
CN107146895A (zh) * | 2017-05-10 | 2017-09-08 | 上海亮仓能源科技有限公司 | 一种车载燃料电池用 Pt 基八面体型纳米晶体阴极催化剂及其制备方法 |
CN107233917A (zh) * | 2017-06-26 | 2017-10-10 | 厦门大学 | 一种钯氢纳米颗粒的制备及在电催化氧化甲酸中的应用 |
-
2018
- 2018-03-20 CN CN201810229551.3A patent/CN110302777A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030178707A1 (en) * | 2002-03-21 | 2003-09-25 | Abbott Donald C. | Preplated stamped small outline no-lead leadframes having etched profiles |
CN102764648A (zh) * | 2011-05-06 | 2012-11-07 | 北京林业大学 | 一种钯催化剂的制备方法,由该方法制备的钯催化剂及应用 |
US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
WO2015108608A2 (en) * | 2013-11-04 | 2015-07-23 | Portland State University | Method of making a metallic composite and use thereof |
CN107146895A (zh) * | 2017-05-10 | 2017-09-08 | 上海亮仓能源科技有限公司 | 一种车载燃料电池用 Pt 基八面体型纳米晶体阴极催化剂及其制备方法 |
CN107233917A (zh) * | 2017-06-26 | 2017-10-10 | 厦门大学 | 一种钯氢纳米颗粒的制备及在电催化氧化甲酸中的应用 |
Non-Patent Citations (4)
Title |
---|
HONGWEN HUANG等: "Understanding of Strain Effects in the Electrochemical Reduction of CO2:Using Pd Nanostructures as an Ideal Platform", 《ANGEW. CHEM. INT. ED. 》 * |
MINGSHANG JIN等: "Palladium Concave Nanocubes with High-Index Facets and Their Enhanced Catalytic Properties", 《ANGEW. CHEM. INT. ED. 》 * |
崔泽琳等: "钯纳米颗粒制备方法的研究进展", 《化学与黏合》 * |
贾欢欢: "钯基金属纳米晶体的可控合成及其CO2电还原性能研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111686719A (zh) * | 2020-06-17 | 2020-09-22 | 青岛科技大学 | 一种钯金属/碳纸催化剂及其制备方法和应用 |
CN114406278A (zh) * | 2021-12-10 | 2022-04-29 | 深圳市百翱生物科技有限公司 | 一种钯纳米立方体颗粒的制备方法 |
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