CN110560082A - 一种自支撑介孔金钯合金薄膜电化学合成氨催化剂及其制备方法 - Google Patents
一种自支撑介孔金钯合金薄膜电化学合成氨催化剂及其制备方法 Download PDFInfo
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- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 title claims abstract description 61
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 11
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
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Abstract
一种自支撑介孔金钯薄膜电化学合成氨催化剂,由如下方法制备:取一块面积为0.1~6cm2的泡沫镍,在盐酸溶液中浸泡除去表面杂质;分别配置浓度为5~50mM的氯金酸和氯钯酸钠溶液;称取2~20mg的PS‑b‑PEO溶解在1~5mL四氢呋喃中,加入1~3mL无水乙醇、0.5~2mL氯金酸溶液和0.5~2mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中浸泡反应;在异丙醇中浸泡除去表面活性剂和未反应的金属前驱体,经过洗涤干燥得到自支撑介孔金钯薄膜催化剂。以及提供自支撑介孔金钯薄膜电化学合成氨催化剂的制备方法。本发明合成的催化剂在电化学合成氨反应中展现了突出的催化活性和稳定性。
Description
(一)技术领域
本发明涉及一种自支撑介孔金钯合金薄膜电化学合成氨催化剂及其制备方法,该催化剂可用于电催化合成氨反应的研究。
(二)背景技术
合成氨工业对人类的生活有着重要的作用。现如今,氨的合成主要运用传统的哈伯-博世工艺,由高纯度的氮气催化加氢合成。由于氮气是一种惰性气体,为了打开氮氮三键,因此用哈伯-博世工艺来合成氨时,在铁基催化剂的催化下,还需在350~550℃和15~35MPa这样的恶劣的条件才能运行。此外,该工艺在合成氨的同时,会消耗大量的能源并排放出大量的二氧化碳。因此,这迫切的需要发展一个可行的合成方法来替代哈伯-博世工艺,来实现在温和的条件下,高效、可持续、经济地生产氨。
电化学合成氨作为一种可供选择的策略,由于其可以在温和的条件下,用电化学的方法将原料氮气和水转化成氨,引起了广泛的研究兴趣。而电化学合成氨的关键是要设计一种高催化活性和高选择性的催化剂。最近的一些研究指出,贵金属特别是金和钯展现出了优异的电化学合成氨的性能,但是实际的产氨速率和法拉第效率依旧无法满足工业化生产(M.Iwamoto,M.Akiyama,K.Aihara,T.Deguchi,ACS Catal.2017,7,6924;S.J.Li,D.Bao,M.M.Shi,B.R.Wulan,J.M.Yan,Q.Jiang,Adv.Mater.2017,29;H.Wang,H.Yu,Z.Wang,Y.Li,Y.Xu,X.Li,H.Xue,L.Wang,Small 2019,15,e1804769;J.Wang,L.Yu,L.Hu,G.Chen,H.Xin,X.Feng,Nat.Commun.2018,9,1795)。为了进一步改善电化学合成氨的性能,调整催化剂的结构和组成是一个有吸引力的策略。多孔贵金属因为拥有孔道结构和高比表面积在催化领域得到了广泛的研究。传统的多孔贵金属合成方法有去合金法和硬模板法,然而,它们通常涉及复杂的合成过程并且难以控制孔隙大小。在我们之前的工作中,我们以嵌段共聚物为软模板,通过胶束自组装的方法合成了一系列介孔铂基材料。不幸的是,大多数多孔金属催化剂在电催化应用中要使用聚合物粘结剂与电极结合,从而导致其导电性和催化活性降低。为了解决这些问题,直接在导电基底上制备多孔金属材料具有广阔的应用前景。最近,我们已经证明了一种胶束辅助置换法能在泡沫镍表面合成介孔铂基薄膜。与铂不同,由于难以控制前驱体的还原速率和胶束中金的生长,在导电基底上制备自支撑多孔金薄膜仍然是一个很大的挑战。
(三)发明内容
本发明涉及一种自支撑介孔金钯合金薄膜电化学合成氨催化剂及其制备方法,利用嵌段共聚物,在泡沫镍上生长介孔金钯薄膜,该材料表现出了很好的电化学合成氨性能,该催化剂可用于电催化合成氨反应的研究。
本发明采用的技术方案是:
一种自支撑介孔金钯薄膜电化学合成氨催化剂,由如下方法制备:
(1)取一块面积为0.1~6cm2的泡沫镍,在浓度为1~6M的盐酸溶液中浸泡5~30min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(2)分别配置浓度为5~50mM的氯金酸和氯钯酸钠溶液备用;
(3)称取2~20mg的PS-b-PEO溶解在1~5mL四氢呋喃中,加入1~3mL无水乙醇、0.5~2mL氯金酸溶液和0.5~2mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应1~40min;
(4)产物在异丙醇中浸泡10~14小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
不同的反应条件会对制备的自支撑介孔金钯薄膜的结构产生重要影响。表面活性剂PS-b-PEO作为胶束软模板,在制备自支撑多孔金钯薄膜中起到了造孔的作用。在反应过程中,泡沫镍作为还原剂和导电基底,起到了重要的作用。
一种自支撑介孔金钯薄膜电化学合成氨催化剂的制备方法,包括如下步骤:
(1)取一块面积为0.1~6cm2的泡沫镍,在浓度为1~6M的盐酸溶液中浸泡5~30min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(2)分别配置浓度为5~50mM的氯金酸和氯钯酸钠溶液备用;
(3)称取2~20mg的PS-b-PEO溶解在1~5mL四氢呋喃中,加入1~3mL无水乙醇、0.5~2mL氯金酸溶液和0.5~2mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应1~40min;
(4)产物在异丙醇中浸泡12小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
进一步,调控泡沫镍面积,氯金酸和氯钯酸钠的浓度和体积,表面活性剂用量,表面活性剂的种类,以及反应时间来调控金钯催化剂的形貌和结构。
在常温常压下进行电化学合成氨反应,性能测试操作过程为:
(1)剪取面积为0.25~1cm2的金钯薄膜作为工作电极;
(2)在H型电解池中进行电化学合成氨性能测试,电解池的一侧为工作电极金钯催化剂和参比电极饱和Ag/AgCl电极组成电解池的阴极,另一侧为对电极石墨棒组成电解池的阳极。在测试之前,将氮气通入电解池的阴极直至电解液中氮气饱和,选择线性扫描循环伏安法和计时电流法的测试程序,用计算机监视工作电极在不同电位下的电流情况。然后用紫外可见分光光度计和氨的标准曲线计算电解反应后电解液中氨的浓度,并计算得出该催化剂的产氨速率和法拉第效率。
本发明所提供的自支撑介孔金钯薄膜电化学合成氨催化剂的可控制备方法的有益效果主要体现在:
(1)合理地利用表面活性剂PS-b-PEO作为软模板和造孔剂,合成的介孔金钯薄膜形貌均一,产率高。
(2)合成方法简单,采用泡沫镍的氧化还原置换法合成,可以在短时间内得到孔径均一的介孔金钯薄膜催化剂。
(3)合成的介孔金钯薄膜催化剂在电化学合成氨反应中展现了突出的催化活性和稳定性,具有很高的应用前景。
(四)附图说明
图1为本发明的具体实施例1介孔金钯薄膜的SEM图。
图2为本发明的具体实施例1介孔金钯薄膜的TEM和HRTEM图
图3为本发明的具体实施例1介孔金钯薄膜的XPS图。
图4为本发明的具体实施例1介孔金钯薄膜的双电层电容图。
图5为本发明的具体实施例1介孔金钯薄膜的电化学合成氨性能图。
图6为本发明的具体实施例1介孔金钯薄膜的稳定性图。
图7为本发明的具体实施例2金钯薄膜的SEM图。
图8为本发明的具体实施例2金钯薄膜的双电层电容图。
图9为本发明的具体实施例3不同反应时间介孔金钯薄膜的SEM图。
(五)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
参照图1~图9,本实施例中,对所述金钯薄膜的电化学合成氨性能测试是在CHI660E电化学工作站上进行的,操作过程为:
第一步、剪取面积为0.25~1cm2的金钯薄膜作为工作电极;
第二步,在H型电解池中进行电化学合成氨性能测试,电解池的一侧为工作电极金钯催化剂和参比电极饱和Ag/AgCl电极组成电解池的阴极,另一侧为对电极石墨棒组成电解池的阳极。在测试之前,将氮气通入电解池的阴极直至电解液中氮气饱和,选择线性扫描循环伏安法和计时电流法的测试程序,用计算机监视工作电极在不同电位下的电流情况。然后用紫外可见分光光度计和氨的标准曲线计算电解反应后电解液中氨的浓度,并计算得出该催化剂的产氨速率和法拉第效率。
实施例1
一种自支撑介孔金钯薄膜电化学合成氨催化剂及其制备方法,所述方法包括如下步骤:
(1)取一块面积为2cm2的泡沫镍,在浓度为3M的盐酸溶液中浸泡15min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(2)分别配置浓度为20mM的氯金酸和氯钯酸钠溶液备用;
(3)称取10mg的PS-b-PEO溶解在3mL四氢呋喃中,加入1.5mL无水乙醇、1.5mL氯金酸溶液和0.5mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应20min;
(4)产物在异丙醇中浸泡12小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
获得的介孔金钯薄膜的SEM图参见图1。获得的介孔金钯薄膜TEM和HRTEM图参见图2。获得的介孔金钯薄膜的XPS图参见图3。获得的介孔金钯薄膜的双电层电容图参见图4。获得的介孔金钯薄膜的电化学合成氨性能图参见图5。获得的介孔金钯薄膜的稳定性图图参见图6。
由SEM图可见,介孔金钯薄膜表面能清晰地看到连续的介孔结构,平均孔径为28nm,薄膜厚度为320nm。由TEM图可见,介孔金钯薄膜表面呈现网络状的介孔结构。由通过HRTEM分析,证明金属形成了面心立方结构,介孔金钯薄膜主要暴露了(111)晶面。通过XPS分析存在零价金和零价钯,金和钯的前驱体都被还原为单质。将介孔金钯薄膜的Au 4f曲线和介孔金薄膜对比,曲线产生了正移;将介孔金钯薄膜的Pd 3d曲线和介孔钯薄膜对比,曲线产生了负移,证明合金结构的形成。根据双电层电容曲线可以看出该材料具有较高的活性比表面积。根据紫外可见分光光度计测试计算得出该催化剂在中性条件下(-0.1V)产氨速率达到了24.02μg h-1mg-1 cat.,法拉第效率达到了18.16%。
实施例2
一种自支撑介孔金钯薄膜电化学合成氨催化剂及其制备方法,所述方法包括如下步骤:
(1)取一块面积为2cm2的泡沫镍,在浓度为3M的盐酸溶液中浸泡15min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(2)分别配置浓度为20mM的氯金酸和氯钯酸钠溶液备用;
(3)称取10mg的F127溶解在3mL四氢呋喃中,加入1.5mL无水乙醇、1.5mL氯金酸溶液和0.5mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应20min;
(4)产物在异丙醇中浸泡12小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
获得的金钯薄膜的SEM图参见图7,获得的金钯薄膜的双电层电容图参见图8。
由SEM图可见,反应形成了金钯薄膜,表面没有观察到孔结构。根据双电层电容曲线可以看出该材料具有较高的活性比表面积。
实施例3
一种自支撑介孔金钯薄膜电化学合成氨催化剂及其制备方法,所述方法包括如下步骤:
(1)取一块面积为2cm2的泡沫镍,在浓度为3M的盐酸溶液中浸泡15min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(2)分别配置浓度为20mM的氯金酸和氯钯酸钠溶液备用;
(3)称取10mg的PS-b-PEO溶解在3mL四氢呋喃中,加入1.5mL无水乙醇、1.5mL氯金酸溶液和0.5mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应1min;
(4)产物在异丙醇中浸泡12小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
获得的金钯薄膜的SEM图参见图9。
由SEM图可见,反应1min时,泡沫镍表面初步形成介孔金钯合金结构。由于反应时间太短,泡沫镍表面未能生长出完整的介孔薄膜结构。
实施例4
一种自支撑介孔金钯薄膜电化学合成氨催化剂及其制备方法,所述方法包括如下步骤:
(1)取一块面积为0.1cm2的泡沫镍,在浓度为1M的盐酸溶液中浸泡5min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(2)分别配置浓度为5mM的氯金酸和氯钯酸钠溶液备用;
(3)称取2mg的PS-b-PEO溶解在1mL四氢呋喃中,加入1mL无水乙醇、0.5mL氯金酸溶液和0.5mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应1min;
(4)产物在异丙醇中浸泡10小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
由于在这个合成过程中,氯金酸和氯钯酸钠浓度太低,反应速率过慢,泡沫镍表面未能生长出均匀的孔结构,金薄膜的厚度很小,很难得到自支撑的介孔金钯薄膜。
实施例5
一种自支撑介孔金钯薄膜电化学合成氨催化剂及其制备方法,所述方法包括如下步骤:
(5)取一块面积为6cm2的泡沫镍,在浓度为6M的盐酸溶液中浸泡30min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(6)分别配置浓度为50mM的氯金酸和氯钯酸钠溶液备用;
(7)称取20mg的PS-b-PEO溶解在5mL四氢呋喃中,加入3mL无水乙醇、2mL氯金酸溶液和2mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应40min;
(8)产物在异丙醇中浸泡14小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
由于在这个合成过程中,氯金酸和氯钯酸钠浓度太高,反应速率过快,泡沫镍表面未能生长出均匀的孔结构,金薄膜的厚度很厚,很难得到自支撑的介孔金钯薄膜。
Claims (3)
1.一种自支撑介孔金钯薄膜电化学合成氨催化剂,其特征在于,由如下方法制备:
(1)取一块面积为0.1~6cm2的泡沫镍,在浓度为1~6M的盐酸溶液中浸泡5~30min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(2)分别配置浓度为5~50mM的氯金酸和氯钯酸钠溶液备用;
(3)称取2~20mg的PS-b-PEO溶解在1~5mL四氢呋喃中,加入1~3mL无水乙醇、0.5~2mL氯金酸溶液和0.5~2mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应1~40min;
(4)产物在异丙醇中浸泡10~14小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
2.一种如权利要求1所述的一种自支撑介孔金钯薄膜电化学合成氨催化剂及其制备方法,其特征在于,所述方法包括如下步骤:
(1)取一块面积为0.1~6cm2的泡沫镍,在浓度为1~6M的盐酸溶液中浸泡5~30min除去表面氧化层和杂质,用乙醇和水洗涤后干燥;
(2)分别配置浓度为5~50mM的氯金酸和氯钯酸钠溶液备用;
(3)称取2~20mg的PS-b-PEO溶解在1~5mL四氢呋喃中,加入1~3mL无水乙醇、0.5~2mL氯金酸溶液和0.5~2mL氯钯酸钠溶液配成反应溶液,将处理好的泡沫镍置于反应溶液中,浸泡反应1~40min;
(4)产物在异丙醇中浸泡10~14小时,除去表面活性剂和未反应的金属前驱体,用水和乙醇洗涤后干燥,得到自支撑介孔金钯薄膜电化学合成氨催化剂。
3.如权利要求2所述的方法,其特征在于,控制氯金酸和氯钯酸钠的浓度和体积,表面活性剂的种类,四氢呋喃的体积,泡沫镍的面积,以及反应时间来控制金钯催化剂的形貌和结构。
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Application publication date: 20191213 |