CN104607186B - 基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法与应用 - Google Patents
基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法与应用 Download PDFInfo
- Publication number
- CN104607186B CN104607186B CN201510058026.6A CN201510058026A CN104607186B CN 104607186 B CN104607186 B CN 104607186B CN 201510058026 A CN201510058026 A CN 201510058026A CN 104607186 B CN104607186 B CN 104607186B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- pdsn
- preparation
- eutectic solvent
- mwcnts
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002904 solvent Substances 0.000 title claims abstract description 17
- 230000005496 eutectics Effects 0.000 title claims abstract description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000019253 formic acid Nutrition 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 238000013019 agitation Methods 0.000 claims description 5
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 4
- 235000019743 Choline chloride Nutrition 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229960003178 choline chloride Drugs 0.000 claims description 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002041 carbon nanotube Substances 0.000 abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000002082 metal nanoparticle Substances 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- 231100000572 poisoning Toxicity 0.000 abstract 1
- 230000000607 poisoning effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 239000002057 nanoflower Substances 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MOGGVIXWTIOANP-UHFFFAOYSA-N [O].OC=O Chemical compound [O].OC=O MOGGVIXWTIOANP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003950 stripping voltammetry Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02E60/50—Fuel cells
Abstract
本发明公开了一种基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法与应用,是一种简单新颖的制备直接甲酸燃料电池用阳极电催化剂的方法,首次以低共熔溶剂为介质,采用化学还原方法来制备。该催化剂的制备方法,工艺简单,操作条件温和、环保,使用低共熔溶剂体系可以明显降低催化纳米颗粒的尺寸,使金属纳米颗粒沿着碳纳米管表面生长并团聚形成了特殊的链状团簇结构,提高了贵金属的电化学活性表面积,同时还有利于增强复合材料催化剂中各组分之间的电荷转移相互作用,从而极大地提高了催化剂对甲酸氧化的电催化活性和稳定性,且具有优良的抗CO毒化的能力。
Description
技术领域
本发明涉及电催化和燃料电池领域,具体是一种基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法,以及在直接甲酸燃料电池中的应用。
背景技术
低共熔溶剂(Deep eutectic solvents,DES)具有蒸汽压低、无毒性、可生物降解、溶解性和导电性优良、电化学稳定窗口宽等独特的物理化学性质,使其成为一种有前途的绿色溶剂而广泛应用于功能纳米材料合成领域。目前,有关以低共熔溶剂为介质制备燃料电池催化剂方面的研究文献报道不多,仅涉及如下的几篇文献报道:(1) 2012年《Journalof Physical Chemistry C》报道了一种以DES为介质电化学形状控制合成高表面能Pt纳米晶的新方法,首次成功合成了{910}和邻近高指数面包围的凹二十四面体Pt纳米晶催化剂,发现它对乙醇氧化表现出比商业Pt黑更高的电催化活性和稳定性;(2) 2012年《Electrochimica Acta》报道以DES为介质采用循环伏安法成功制备了一种形状和尺寸均一、且具有尖锐单晶花瓣及高密度原子台阶的Pt纳米花。所制得的刺状结构Pt纳米花对乙醇氧化表现出比其他形状Pt纳米花和商业Pt黑催化剂更高的电催化活性和稳定性;(3)2013年《Chemical Communications》报道以DES为介质采用电化学方法成功合成了{771}高指数面包围的六十面体Pt纳米晶催化剂,发现它对乙醇氧化表现出比商业Pt黑更高的电催化活性和稳定性;(4) 2015年《Journal of Materials Chemistry A》报道了以DES为介质通过电化学方法制备的具有高甲醇电氧化性能的Au@Pd核壳纳米颗粒催化剂。由此可见,DES作为一种有前途的绿色溶剂已开始在燃料电池电催化剂制备研究领域受到了人们的关注。然而,上述文献报道的DES中燃料电池催化剂的制备均局限于采用电化学方法,这将使催化剂的大规模制备及商业化应用受到一定的限制。有关以DES为介质通过化学还原方法来制备Pd基催化剂并应用于直接甲酸燃料电池的研究尚未见文献和专利报道。
发明内容
本发明的目的是提供一种基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法与应用,该制备方法工艺简单,操作条件温和、环保;该方法制备的催化剂对甲酸氧化表现出电催化活性好、稳定性高和抗CO毒化能力强的特性。
实现本发明目的的技术方案是:
一种基于低共熔溶剂(DES)的多壁碳纳米管(MWCNTs)载PdSn催化剂的制备方法,包括如下步骤:
1)在20 mL DES中加入10 mg酸化的MWCNTs,超声分散2 h;
2)超声分散后,加入质量比为PdSn/MWCNTs = 1/4的56.4 mM 的PdCl2和42.1 mM的SnCl2的DES溶液,磁力搅拌1 h;
3)磁力搅拌后,加入100 mg NaBH4固体,继续搅拌10 min后将所得悬液移入25 mL反应釜中,80~200℃下反应12 h,反应产物经离心、洗涤和真空干燥后,得到MWCNTs载PdSn催化剂。
步骤1)和2)中所述DES为氯化胆碱/尿素。
步骤2)中加入Pd/Sn的质量比为Pd/Sn = 1/0.1~1。
应用上述制备方法制得的多壁碳纳米管载PdSn催化剂。
上述制得的多壁碳纳米管载PdSn催化剂应用于直接甲酸燃料电池。
燃料电池电催化剂中催化纳米颗粒的尺寸和形状与制备催化剂所用的溶剂体系密切相关。本发明提供了一种简单新颖的制备直接甲酸燃料电池用阳极电催化剂的方法,首次以低共熔溶剂为介质,采用化学还原方法来制备多壁碳纳米管载PdSn催化剂。该催化剂的制备方法,工艺简单,操作条件温和、环保,使用低共熔溶剂体系可以明显降低催化纳米颗粒的尺寸,使金属纳米颗粒沿着碳纳米管表面生长并团聚形成了特殊的链状团簇结构,提高了贵金属的电化学活性表面积,同时还有利于增强复合材料催化剂中各组分之间的电荷转移相互作用,从而极大地提高了催化剂对甲酸氧化的电催化活性和稳定性,且具有优良的抗CO毒化的能力。
附图说明
图1为实施例DES中制备多壁碳纳米管载PdSn催化剂的方框图。
图2为实施例DES中制备的MWCNTs载PdSn(a)、MWCNTs载Pd(b)和水体系中制备的MWCNTs载Pd(c)催化剂的XRD图。
图3为实施例DES中制备的MWCNTs载PdSn(A)、MWCNTs载Pd(B)和水体系中制备的MWCNTs载Pd(C)催化剂的TEM图。
具体实施方式
下面结合附图和实施例对本发明内容作进一步的说明,但不是对本发明的限定。
实施例
参照图1,以氯化胆碱/尿素DES为介质制备多壁碳纳米管(MWCNTs)载PdSn催化剂,具体过程如下:在20 mL氯化胆碱/尿素DES中加入10 mg经浓H2SO4或HNO3酸化处理的MWCNTs,超声分散2 h后,加入质量比为PdSn/MWCNTs = 1/4的56.4 mM 的PdCl2和42.1 mM的SnCl2的DES溶液,控制所加入Pd/Sn的质量比为Pd/Sn = 1/0.1~1,磁力搅拌1 h后加入100 mg NaBH4固体,继续搅拌10 min后将所得悬液移入25 mL反应釜中,80~200℃下反应12 h,反应产物经离心、洗涤和真空干燥后,得到MWCNTs载PdSn催化剂。
XRD分析表明,该催化剂中Pd纳米颗粒的尺寸显著降低,其平均尺寸为2.3 nm,明显小于同样条件下制备的MWCNTs载Pd和水体系中制备的MWCNTs载Pd催化剂中Pd纳米颗粒的尺寸(分别为4.1 nm和6.2 nm)。此外,TEM分析表明,DES中制备的MWCNTs载PdSn催化剂,金属纳米颗粒沿着碳纳米管表面生长并聚集形成了表面粗糙的特殊链状团簇结构,这有利于提高催化剂的电化学活性表面积和电催化性能。图2和图3分别给出了上述三种催化剂的XRD图和TEM图。
通过循环伏安法和计时电流法比较了DES中制备的MWCNTs载PdSn、MWCNTs载Pd和水体系中制备的MWCNTs载Pd催化剂的电化学性质以及对甲酸氧化的电催化性能。结果表明,DES中制备的MWCNTs载PdSn催化剂具有较高的电化学活性表面积,其对甲酸氧化的电催化活性分别为同样介质中制备的MWCNTs载Pd和水体系中制备的MWCNTs载Pd催化剂的1.8和3.0倍。此外,DES中制备的MWCNTs载PdSn催化剂还表现出优良的甲酸氧化电化学稳定性。
通过电化学CO溶出伏安法比较了DES中制备的MWCNTs载PdSn、MWCNTs载Pd和水体系中制备的MWCNTs载Pd催化剂的抗CO毒化的性能。结果指出,CO在DES中制备的MWCNTs载PdSn催化剂上的起始氧化电位分别比同样介质中制备的MWCNTs载Pd和水体系中制备的MWCNTs载Pd催化剂负移了60和140 mV,这表明DES中制备的MWCNTs载PdSn催化剂具有优良的抗CO毒化的能力。
Claims (3)
1.一种基于低共熔溶剂的多壁碳纳米管载PdSn催化剂的制备方法,其特征是,包括如下步骤:
1)在20 mL 低共熔溶剂DES中加入10 mg酸化的多壁碳纳米管MWCNTs,超声分散2 h;
2)超声分散后,加入质量比为PdSn/MWCNTs = 1/4的56.4 mM的PdCl2和42.1 mM的SnCl2的DES溶液,磁力搅拌1 h;
3)磁力搅拌后,加入100 mg NaBH4固体,继续搅拌10 min后将所得悬液移入25 mL反应釜中,80~200℃下反应12 h,反应产物经离心、洗涤和真空干燥后,得到MWCNTs载PdSn催化剂;
步骤1)和2)中所述DES为氯化胆碱/尿素;
步骤2)中加入Pd/Sn的质量比为Pd/Sn = 1/0.1~1。
2.用权利要求1所述制备方法制得的多壁碳纳米管载PdSn催化剂。
3.权利要求2所述多壁碳纳米管载PdSn催化剂在直接甲酸燃料电池中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510058026.6A CN104607186B (zh) | 2015-02-05 | 2015-02-05 | 基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510058026.6A CN104607186B (zh) | 2015-02-05 | 2015-02-05 | 基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104607186A CN104607186A (zh) | 2015-05-13 |
CN104607186B true CN104607186B (zh) | 2017-02-22 |
Family
ID=53141990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510058026.6A Expired - Fee Related CN104607186B (zh) | 2015-02-05 | 2015-02-05 | 基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104607186B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10727496B2 (en) * | 2016-07-14 | 2020-07-28 | Ford Global Technologies, Llc | Fuel cell oxidation reduction reaction catalyst |
CN106784901A (zh) * | 2016-12-27 | 2017-05-31 | 广西师范大学 | 基于多壁碳纳米管载PdCd合金催化剂及其制备方法和应用 |
CN108311145A (zh) * | 2017-01-17 | 2018-07-24 | 中国科学院上海高等研究院 | 碳载钯锡纳米合金催化剂的制备及其在二氧化碳电催化还原中的应用 |
CN108346808B (zh) * | 2018-03-09 | 2020-07-17 | 青岛大学 | 一种钯锡纳米链网状催化剂及其制备方法和应用 |
CN108878911B (zh) * | 2018-06-19 | 2021-06-08 | 广西师范大学 | 一种基于低共熔溶剂的氮掺杂碳纳米管载Pt催化剂及其制备方法与应用 |
CN110201670B (zh) * | 2019-05-21 | 2020-05-29 | 山东大学 | 基于三氯化铁/尿素低共熔溶剂的镍铁双金属氢氧化物/泡沫镍催化剂、其制备方法及应用 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2039669A1 (en) * | 2007-09-19 | 2009-03-25 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Use of a mixture of an ordered intermetallic compound and an inert material as a catalyst and corresponding hydrogenation processes |
CN102078811B (zh) * | 2010-12-26 | 2013-02-13 | 南京师范大学 | 均相沉淀-原位还原法制备炭载Pd纳米粒子催化剂的方法 |
CN102489314B (zh) * | 2011-12-07 | 2013-10-23 | 天津大学 | 用于甲醇、乙醇燃料电池的石墨烯负载双金属纳米粒子及制备方法 |
-
2015
- 2015-02-05 CN CN201510058026.6A patent/CN104607186B/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN104607186A (zh) | 2015-05-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104607186B (zh) | 基于低共熔溶剂的多壁碳纳米管载PdSn催化剂及其制备方法与应用 | |
CN104538642B (zh) | 一种直接甲醇燃料电池硫掺杂碳纳米管载Pt催化剂及其制备方法 | |
Kakaei et al. | Fabrication of Pt–CeO2 nanoparticles supported sulfonated reduced graphene oxide as an efficient electrocatalyst for ethanol oxidation | |
EP3027308B1 (en) | Method for forming noble metal nanoparticles on a support | |
Zhang et al. | Cu3P/RGO promoted Pd catalysts for alcohol electro-oxidation | |
Liu et al. | Manganese dioxide coated graphene nanoribbons supported palladium nanoparticles as an efficient catalyst for ethanol electrooxidation in alkaline media | |
Moura Souza et al. | Niobium: a promising Pd co-electrocatalyst for ethanol electrooxidation reactions | |
CN105845948B (zh) | 一种花状铜/氧化铜微纳米复合材料负载贵金属燃料电池催化剂的制备方法 | |
Li et al. | Enhanced activity and durability of platinum anode catalyst by the modification of cobalt phosphide for direct methanol fuel cells | |
CN108470920A (zh) | 一种用于酸性介质的石墨烯负载铂钴钨合金纳米粒子复合催化剂及其制备方法 | |
Urbańczyk et al. | NiPt sinter as a promising electrode for methanol electrocatalytic oxidation | |
CN108878911A (zh) | 一种基于低共熔溶剂的氮掺杂碳纳米管载Pt催化剂及其制备方法与应用 | |
CN104209122A (zh) | 一种PtRu/C催化剂及其制备方法 | |
Afzali et al. | Design of PdxIr/g-C3N4 modified FTO to facilitate electricity generation and hydrogen evolution in alkaline media | |
Li et al. | A review of approaches for the design of high-performance electrocatalysts for ethanol electrooxidation | |
CN103191757B (zh) | 一种PdNiW/C三元合金纳米催化剂及其制备方法 | |
Karimi et al. | Application of quasihexagonal Pt@ PdS2-MWCNT catalyst with high electrochemical performance for electro-oxidation of methanol, 2-propanol, and glycerol alcohols for fuel cells | |
Salarizadeh et al. | Comparison of methanol oxidation reaction process for NiCo2O4/X (X= rGO, MWCNTs, HCNs) nanocatalyst | |
Yu et al. | Recent progress on reduced graphene oxide supported Pt-based catalysts and electrocatalytic oxidation performance of methanol | |
CN104607205B (zh) | 基于低共熔溶剂的多壁碳纳米管载PtCu催化剂及其制备方法与应用 | |
CN110783583A (zh) | 三维Au-GQDs@AgPt蛋黄壳结构纳米复合材料及其制备和应用 | |
CN108746659B (zh) | 一种花状AgPd纳米合金及制备和使用方法 | |
CN106784901A (zh) | 基于多壁碳纳米管载PdCd合金催化剂及其制备方法和应用 | |
Altuner et al. | Ternary/quaternary nanomaterials for direct alcohol fuel cells | |
CN104607206B (zh) | 基于低共熔溶剂的多壁碳纳米管载PtCo催化剂及其制备方法与应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170222 |
|
CF01 | Termination of patent right due to non-payment of annual fee |