CN108927185A - 一种杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂及其制备方法 - Google Patents
一种杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 22
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 title claims abstract description 17
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
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- YYMZGBPPXGPQLH-UHFFFAOYSA-N benzoic acid;iron Chemical compound [Fe].OC(=O)C1=CC=CC=C1 YYMZGBPPXGPQLH-UHFFFAOYSA-N 0.000 claims description 2
- 235000007144 ferric diphosphate Nutrition 0.000 claims description 2
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- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 claims description 2
- 229940036404 ferric pyrophosphate Drugs 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
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- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical group C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
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- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 5
- 239000011943 nanocatalyst Substances 0.000 abstract description 5
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 abstract description 4
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- 238000004090 dissolution Methods 0.000 description 6
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 5
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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Abstract
本发明属于纳米新材料制备技术领域,涉及一种杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂。该纳米催化剂以聚膦腈纳米管为杂原子掺杂碳纳米管前驱体,以有机铁盐或无机铁盐为铁元素前驱体。经过聚膦腈纳米管吸附铁元素前驱体,惰性气氛下一步高温碳化,得杂原子掺杂碳纳米管负载磷化铁纳米粒子复合材料。该复合材料具有优异的氧还原催化性能,其氧还原催化剂催化活性和商业化Pt/C催化剂接近,其更廉价易得,同时,其催化耐久性、耐甲醇毒性等特性较商业化Pt/C催化剂更优。
Description
技术领域:
本发明属于纳米新材料制备技术领域,涉及的是一种纳米氧还原催化剂,具体是一种杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂及其制备工艺。
背景技术:
燃料电池、金属空气电池等电化学新能源装置具有清洁、高效等特点。当前社会人们的环保意识不断增强,同时新能源汽车、可移动电子设备高速发展,给燃料电池、金属空气电池等新能源装置带来了前所未有的发展机遇。然而,作为这些电化学新能源装置阴极的重要组成部分,氧还原催化剂活性不足,限制了这些新能源装置的发展。贵金属催化剂具有优良的催化活性,然而,其价格高昂、催化耐久性差、易中毒等特点,限制了燃料电池等电化学新能源装置的推广。因此,开发高效、廉价的新型催化剂替代贵金属催化剂成为必然选择。
过渡金属化合物具有较好的催化活性,使其成为新型燃料电池催化剂的有力替代品。然而,过渡金属化合物作为燃料电池催化剂也存在缺点:(1)过渡金属化合物的导电性差,需要将其负载到一定的导电载体上;(2)需要将过渡金属化合物微纳米化以增加活性位点数量,从而增加催化剂催化效果。为解决过渡金属化合物催化剂的上述缺点,一般将过渡金属化合物和碳材料复合,并通过一定的工艺控制,得到过渡金属化合物微纳米粒子分散在碳载体上的复合催化剂。
经过对现有技术的检索发现,目前在制备过渡金属化合物-碳纳米复合材料过程中,仍面临材料微纳米结构、化学结构等可控性差的问题。中国专利文献号CN106252673A,公开日2016-12-21,公开一种基于天然植物组织的Fe-N/C氧还原反应催化剂的制备方法,是将天然植物组织粉碎后,水热碳化,低温冻干,在惰性气氛下于700~ 1000℃进行高温焙烧,所得产物与铁源掺杂,再次低温冻干,高温焙烧,通过以上步骤制得铁氮掺杂的多孔碳材料氧还原催化剂。中国专利文献号CN107742732A,公开日2018-02-27,公开一种含铁氧还原催化剂的制备方法。该发明将可溶性铁盐、KB、含氮有机物以及水混合进行水热反应后研磨,然后进行第一煅烧,第一煅烧产物经无机酸洗涤后进行第二煅烧,得到含铁氧还原催化剂。该方法所得催化剂微纳米结构均一性差,化学结构可控性较差,影响材料氧还原催化性能。
发明内容:
本发明的目的在于克服现有技术存在的缺点,提出一种杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂及其制备方法,该纳米催化剂以聚膦腈纳米管为杂原子掺杂碳纳米管前驱体,以有机铁盐或无机铁盐为铁元素前驱体,经过聚膦腈纳米管吸附铁元素前驱体,惰性气氛下一步高温碳化,制得杂原子掺杂碳纳米管负载磷化铁纳米粒子复合材料,该复合材料具有优异的氧还原催化性能,其氧还原催化剂催化活性和商业化Pt/C催化剂接近,其更廉价易得,同时,其催化耐久性、耐甲醇毒性等特性较商业化Pt/C催化剂更优。
为了实现上述目的,本发明通过以下技术方案实现:
(1)以六氯环三磷腈和4,4’-二羟基二苯砜为共聚单体,四氢呋喃为溶剂,在缚酸剂存在条件下,经超声反应制备聚膦腈纳米管;
(2)将铁盐化合物和聚膦腈纳米管分别溶解或分散在溶剂中,使聚膦腈纳米管吸附铁盐化合物,吸附后的固体产物经离心、洗涤、干燥得吸附铁盐化合物的聚膦腈纳米管;
(3)将吸附铁盐化合物的聚膦腈纳米管在惰性气氛下煅烧,得杂原子掺杂碳纳米管负载磷化铁纳米氧还原催化剂。
本发明涉及的步骤(1)中六氯环三磷腈和4,4’-二羟基二苯砜的摩尔比为1:2~1:5。
本发明涉及的步骤(1)中缚酸剂为三乙胺、吡啶或C1~C3的烷氧基吡啶。
本发明涉及的步骤(1)中缚酸剂和六氯环三磷腈的摩尔比为 1:0.3~1:0.01。
本发明涉及的步骤(1)中反应温度为20~60℃,所述反应时间为2~36h。
本发明涉及的步骤(2)中的铁盐化合物为氯化铁、硝酸铁、硫酸铁、磷酸铁、氯化亚铁、硝酸亚铁、硫酸亚铁、乙酸铁、草酸铁、乙酰丙酮铁、柠檬酸铁、焦磷酸铁、二茂铁、苯甲酸铁的一种或多种,或者其水合物的一种或多种。
本发明涉及的步骤(2)中的溶剂为水、甲醇、乙醇、乙二醇或其混合物。
本发明涉及的步骤(2)中的铁盐为化合物和聚膦腈纳米管的质量比为0.01:1~0.5:1。
本发明涉及的步骤(3)中的惰性气氛为氮气、氩气或者其混合气氛。
本发明涉及的步骤(3)中的煅烧温度为600~1300℃,所述煅烧时间为0.1~3h。
本发明与现有技术相比,制备的杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂的工艺简便,制备效率高。该催化剂中的碳纳米管具有均一的一维结构,且磷化铁纳米粒子尺寸均匀,尺寸为 10~25nm,且具有优异的氧还原催化性能,其氧还原起始还原电位接近商业化Pt/C催化剂,且极限电流密度大于商业化Pt/C催化剂,产品应用环境友好。
附图说明:
图1为本发明涉及的纳米催化剂的透射电子显微镜照片示意图。
图2为本发明涉及的纳米催化剂的氮气吸附脱吸附曲线示意图。
图3为本发明涉及的纳米催化剂的氧还原催化性能曲线示意图。
具体实施方式:
下面通过实施例对本发明作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
本实施例通过以下步骤实现杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂的制备:
步骤一,称取0.5g六氯环三磷腈和1.1g 4,4’-二羟基二苯砜加入到装有100mL四氢呋喃的单口烧瓶中,50℃超声水浴条件下使六氯环三磷腈和4,4’-二羟基二苯砜溶解;再向溶液中缓慢滴加2mL三乙胺,保持反应温度为50℃,反应12h;反应结束后,通过离心、水洗、干燥,得白色聚膦腈纳米管;
步骤二,称取四水合氯化亚铁0.1g溶于1mL水中,充分溶解后将该溶液加入到50mL浓度为10mg/mL的聚膦腈纳米管的水分散液中;搅拌12h使聚膦腈纳米管充分吸附氯化亚铁四水合物;反应结束后,经离心、水洗、干燥得吸附四水合氯化亚铁的聚膦腈纳米管;
步骤三,取0.5g步骤二制备的吸附有四水合氯化亚铁的聚膦腈纳米管置于管式炉中,通过连续三次抽真空和充氮气过程,置换掉管式炉腔体内的氧气;以3℃/min升温速度升温至800℃,恒温2h,得黑色催化剂粉末,即杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂。
实施例2
本实施例通过以下步骤实现杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂的制备:
步骤一,称取0.5g六氯环三磷腈溶解于50mL四氢呋喃中,充分溶解后,在40℃超声水浴条件下,将该溶液滴加至溶解有1.1g 4,4’- 二羟基二苯砜和2mL吡啶的四氢呋喃溶液中;保持反应温度为 40℃,反应12h;反应结束后,通过离心、水洗、干燥,得白色聚膦腈纳米管;
步骤二,称取四水合氯化亚铁0.1g溶于1mL水中,充分溶解后将该溶液加入到50mL浓度为10mg/mL的聚膦腈纳米管的水分散液中;搅拌12h使聚膦腈纳米管充分吸附氯化亚铁四水合物;反应结束后,经离心、水洗、干燥得吸附四水合氯化亚铁的聚膦腈纳米管;
步骤三,取0.5g步骤二制备的吸附有四水合氯化亚铁的聚膦腈纳米管置于管式炉中,通过连续三次抽真空、充氮气过程,置换掉管式炉腔体内的氧气;以3℃/min升温速度升温至900℃,恒温1h,得黑色催化剂粉末,即杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂。
实施例3
本实施例通过以下步骤实现杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂的制备:
步骤一,称取0.5g六氯环三磷腈溶解于50mL四氢呋喃中,充分溶解后,在40℃超声水浴条件下,将该溶液滴加至溶解有1.1g 4,4’- 二羟基二苯砜和2mL吡啶的四氢呋喃溶液中;保持反应温度为 40℃,反应12h;反应结束后,通过离心、水洗、干燥,得白色聚膦腈纳米管;
步骤二,称取醋酸铁0.1g溶于1mL乙醇中,充分溶解后将该溶液加入到50mL浓度为10mg/mL的聚膦腈纳米管的乙醇分散液中;搅拌6h使聚膦腈纳米管充分吸附醋酸铁;反应结束后,经离心、水洗、干燥得吸附醋酸铁的聚膦腈纳米管;
步骤三,取0.5g步骤二制备的吸附有醋酸铁的聚膦腈纳米管置于管式炉中,通过连续三次抽真空、充氮气过程,置换掉管式炉腔体内的氧气;以3℃/min升温速度升温至900℃,恒温1h,得黑色催化剂粉末,即杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂。
Claims (10)
1.一种杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂的制备方法,其特征在于,包括以下步骤:
(1)以六氯环三磷腈和4,4’-二羟基二苯砜为共聚单体,四氢呋喃为溶剂,在缚酸剂存在条件下,经超声反应制备聚膦腈纳米管;
(2)将铁盐化合物和聚膦腈纳米管分别溶解或分散在溶剂中,使聚膦腈纳米管吸附铁盐化合物,吸附后的固体产物经离心、水洗、干燥得吸附铁盐化合物的聚膦腈纳米管;
(3)将吸附铁盐化合物的聚膦腈纳米管在惰性气氛下煅烧,制得杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中六氯环三磷腈和4,4’-二羟基二苯砜的摩尔比为1:2~1:5。
3.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中缚酸剂为三乙胺、吡啶或C1~C3的烷氧基吡啶。
4.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中缚酸剂和六氯环三磷腈的摩尔比为1:0.3~1:0.01。
5.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中反应温度为20~60℃,所述反应时间为2~36h。
6.根据权利要求1所述的制备方法,其特征在于,所述步骤(2)中的铁盐化合物为氯化铁、硝酸铁、硫酸铁、磷酸铁、氯化亚铁、硝酸亚铁、硫酸亚铁、乙酸铁、草酸铁、乙酰丙酮铁、柠檬酸铁、焦磷酸铁、二茂铁、苯甲酸铁的一种或多种,或者其水合物的一种或多种。
7.根据权利要求1所述的制备方法,其特征在于,所述步骤(2)中的溶剂为水、甲醇、乙醇、乙二醇或其混合物;
优选的,所述铁盐化合物和聚膦腈纳米管的质量比为0.01:1~0.5:1。
8.根据权利要求1所述的制备方法,其特征在于,所述步骤(3)中的惰性气氛为氮气、氩气或者其混合气氛;
优选的,所述煅烧温度为600~1300℃,所述煅烧时间为0.1~3h。
9.采用权利要求1~8中任一项所述的方法制备得到的杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂,其特征是:催化剂中的碳纳米管具有均一的一维结构,且磷化铁纳米粒子尺寸均匀,尺寸为10~25nm。
10.如权利要求9所述的杂原子掺杂碳纳米管负载磷化铁纳米粒子的氧还原催化剂,在制备燃料电池中的应用。
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