CN111560627B - 一种星状结构金纳米晶体及制备方法和应用 - Google Patents
一种星状结构金纳米晶体及制备方法和应用 Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 80
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 79
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 76
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 48
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Abstract
本发明公开了一种星状结构金纳米晶体及制备方法和应用,所述星状结构金纳米晶体的制备方法包括制备低共熔溶剂、配制镀金液、玻碳电极预处理以及制备纳米晶体;所述星状结构金纳米晶体的晶体结构为二十面体的每一个面上外延生长一个三角锥,其表面密勒指数由{331}及邻近的{hhl}高指数晶面构成;所述星状结构金纳米晶体的应用是指作为电化学固氮催化剂在合成氨领域的应用。本发明的制备方法可控,简单易行,能够准确调控金纳米晶体的形貌;所制备的二十面星状结构金纳米晶体具有高效的电催化氮还原合成氨性能,具有重大的应用价值。
Description
技术领域
本发明涉及一种星状结构金纳米晶体及制备方法和应用,具体涉及一种二十面星状结构金纳米晶体及制备方法和电化学固氮领域的应用。
背景技术
氨(NH3)是世界上最重要的无机化合物之一,是制造化肥、染料、药物等重要化学品的原料或中间体。此外,氨分子中氢的含量为17.6wt%(高于甲醇分子中氢的含量:12.5wt%),是一种潜在的储氢载体,有望成为未来储氢的新策略。目前,工业上合成氨主要采用传统Haber-Bosch法,但该工艺需要在高温(400-500℃)和高压(200-300atm)条件下进行,是一个高成本、高能耗、高污染的生产过程,即每生产1吨的氨需消耗能量34GJ,同时产生2吨的CO2温室气体。近年来,随着能源和环境问题日益严重,开发一种在常温常压下可替代传统Haber-Bosch法的低能耗和清洁的合成氨方法迫在眉睫。电催化氮还原反应(NRR)利用可再生能源(如太阳能、风能等)作为驱动力在常温常压下将氮气和水反应生产氨,是一种绿色环保、可持续的固氮方法。然而,电催化氮还原合成氨依然面临两个严峻的问题,(1)反应动力学缓慢:因N≡N三键十分稳定(键能:945kJ mol-1),N-N键断裂非常困难,从而导致氮还原反应动力学极其缓慢。(2)析氢反应(HER)竞争限制:当NRR在水溶液中进行时,氮还原反应电位与水的析氢反应电位十分接近,二者存在竞争关系,从而显著降低了氮还原性能和法拉第效率。因此,开发一种能够高效活化N2分子并有效抑制析氢反应的催化剂成为电催化氮还原合成氨的关键。
金(Au)是一种潜在的电催化氮还原合成氨催化剂,因其优异的电催化性能以及对析氢反应抑制作用,从而显著提高NRR性能。例如,当金纳米催化剂表面为高指数晶面时,可显著提高电催化NRR性能。这主要归因于高指数晶面具有高密度的台阶原子或扭结原子,它们具有较低的配位数在电催化氮还原反应中充当活性位点,从而促进NRR性能。因此,制备表面为高指数晶面结构的纳米晶催化剂是显著提高电催化氮还原性能的有效途径。然而,由于高指数晶面具有很高的表面能,在晶体生长过程中受到热力学上最低总表面能的限制,导致它们在生长过程中趋于消失,最终仅获得由低表面能的低指数晶面({111}或{100})围成的纳米晶体,如八面体和立方体等。
最近研究发现,一种绿色、新型离子液体类似物——低共熔溶剂(Deep EutecticSolvents,DES)因其宽的电化学窗口及富含特性吸附物质,在高指数晶面结构金属纳米晶体的电化学形状控制合成方面表现出巨大的潜力。低共熔溶剂是一种低共熔混合物,通常由季铵盐和氢键给体(如尿素、羧酸、多元醇等)按一定配比混合形成,因其优异的物理化学性质,低共熔溶剂已引起了世界各国研究者们广泛关注,在分离技术、有机合成、金属有机以及功能材料制备等领域有着潜在的应用前景。
发明内容
发明目的:本发明的第一个目的提出一种星状结构金纳米晶体的制备方法,能够可控地制备二十面星状结构金纳米晶体;本发明的第二个目的是提出基于上述制备方法所制备的星状结构金纳米晶体;本发明的第三个目的是提出上述星状结构金纳米晶体的应用。
技术方案:本发明所采用的技术方案如下:
一种星状结构金纳米晶体的制备方法,包括如下步骤:
(1)制备低共熔溶剂:将氯化胆碱和脲混合于烧杯中,密封,60~80℃搅拌至无色液体,制得氯化胆碱-脲基低共熔溶剂;
(2)配制镀金液:将氯金酸溶于步骤(1)所制备的低共熔溶剂中,60~80℃配制成镀金液,25~30℃陈化至无色;
(3)玻碳电极预处理:使用玻碳电极为工作电极,使用氧化铝研磨粉对玻碳电极进行抛光处理,超声清洗后备用,其目的是为了除去电极表面的氧化铝;
(4)制备星状结构金纳米晶体:将步骤(3)中的工作电极置于盛有步骤(2)镀金液的三电极电解池,参比电极为铂丝电极,对电极为铂片电极,运用双电位阶跃法调节成核电位(EN)、成核时间(tN)、生长电位(EG)和生长时间(tG),沉积温度60~80℃,制得星状结构金纳米晶体。
其中,步骤(1)中,氯化胆碱和脲的摩尔比为2:3~1:3。
其中,步骤(2)中,镀液中氯金酸的浓度为10~30mM。
其中,步骤(2)中,陈化时间为3个月以上,优选4个月~5个月。
其中,步骤(3)中,氧化铝研磨粉粒径为0.3~5.0μm,研磨时间为3~5min,超声清洗次数为4~6次。
其中,步骤(4)中,成核电位(EN)为-0.95~-0.1V,成核时间(tN)为0.2~0.3s,生长电位(EG)为-0.53~-0.57V,生长时间(tG)为300~900s。
本发明的制备方法以非水体系低共熔溶剂为介质,在不添加任何表面活性剂的情况下,运用双电位阶跃法制备二十面星状结构金纳米晶体。其中,陈化时间对金纳米晶体的生长起到一定的作用,能够促进二十面星状结构的形成。成核电位(EN)选择为镀金液中金前驱体在玻碳电极上的还原峰电位附近,生长电位(EG)选择为镀金液中金前驱体在玻碳电极上的起始还原电位附近。
上述制备方法所制备的二十面星状结构金纳米晶体,其表面原子排布利用扫描电子显微镜(SEM)对步骤(4)沉积得到的产物进行表征,获得其形貌以及纳米粒子在工作电极表面的分散程度;利用透射电子显微镜(TEM)对步骤(4)沉积得到的产物进行表征,获得其表面原子排布特征,即晶体表面的密勒指数。根据扫描电子显微镜和高分辨率透射电子显微镜表征结果,通过Shape、Materials Studio等专业建模软件建立晶体模型,进一步从理论上验证以及确定所制备金纳米晶体表面所暴露的原子排列规律,其晶体结构为二十面体的每一个面上外延生长一个三角锥,其表面密勒指数由{331}及邻近的{hhl}高指数晶面构成。
其中,所述二十面星状结构金纳米晶体的粒径为300~500nm。
上述二十面星状结构金纳米晶体作为电化学固氮催化剂在合成氨领域的应用也在本发明保护范围之内,在常温常压下研究其电化学固氮反应的催化性能,使用紫外-可见光谱法对电催化氮还原性能产物进行检测,计算其产氨速率和法拉第效率。
有益效果:与现有技术相比,本发明具有以下显著优点:
1、本发明提供了一种绿色新型的、以非水体系低共熔溶剂为介质,在不添加任何表面活性剂的情况下,运用双电位阶跃法制备二十面星状结构金纳米晶体的制备方法;
2、本发明的制备方法可控,简单易行,能准确调控金纳米晶体的形貌;
3、本发明的二十面星状结构金纳米晶体表面为{hhl}高指数晶面,具有高密度的台阶原子,提供了电催化氮还原反应的活性位点;
4、本发明的二十面星状结构金纳米晶体具有高效的电催化氮还原合成氨性能,其产氨速率高达49.3μg h-1cm-2,法拉第效率高达28%,具有重大的应用价值。
附图说明
图1为本发明实施例1制备的二十面星状结构金纳米晶体的SEM图,其中左上插图为高倍率SEM图;
图2为本发明制备的二十面星状结构金纳米晶体的TEM图,其中(a)为实施例1的TEM图,(b)为(a)的局部高倍率TEM图,(c)为实施例2的TEM图,(d)为实施例3的TEM图;
图3为本发明实施例4氮还原反应在不同反应电位下的i-t曲线;
图4为本发明实施例1制备的二十面星状结构金纳米晶体在不同电位下氮还原反应产物的紫外吸收光谱;
图5为本发明实施例1制备的二十面星状结构金纳米晶体在不同电位下氮还原反应的产氨速率和法拉第效率;
图6为本发明对比例的球状商业金粉的SEM图;
图7为本发明实施例1制备的二十面星状结构金纳米晶体和对比例的球状商业金粉在-0.4V电位下氮还原反应产物的紫外吸收光谱;
图8为本发明实施例1制备的二十面星状结构金纳米晶体和对比例的球状商业金粉在-0.4V电位下氮还原反应的产氨速率和法拉第效率。
具体实施方式
下面结合附图和实施例对本发明的技术方案作进一步的说明。
实施例1
本实施例的二十面星状结构金纳米晶体通过如下步骤制备得到:
(1)制备氯化胆碱-脲基低共熔溶剂:将氯化胆碱和脲按摩尔比为2:3添加到圆底烧瓶中并密封,置于60℃甘油浴中并磁力搅拌至无色液体,置于真空干燥箱中60℃下干燥12h,备用;
(2)配制镀金液:称取1.24g的氯金酸溶于100mL步骤(1)所制备的低共熔溶剂中,配制成含有30mM氯金酸的氯化胆碱-脲基低共熔溶剂溶液,置于28℃的恒温箱中陈化4个月至无色,备用;
(3)玻碳电极预处理:使用玻碳电极(Φ=6mm)为工作电极,在每次电沉积前分别使用1.0μm和0.3μm粒径的氧化铝研磨粉对玻碳电极进行抛光处理,研磨时间3min;然后在超纯水浴中超声清洗,清洗5次,除去电极表面的氧化铝研磨粉,以获得新鲜的玻碳工作电极表面,备用;
(4)制备星状结构金纳米晶体:将步骤(3)处理过的工作电极置于盛有10mL步骤(2)配制的镀液的三电极电解池中,参比电极和对电极分别为铂丝电极和铂片电极,运用双电位阶跃法调节成核电位(EN)为-0.97V、成核时间(tN)为0.25s、生长电位(EG)为-0.55V和生长时间(tG)为500s,沉积温度60℃,得二十面星状结构金纳米晶体。
该实施例所制备的二十面星状结构金纳米晶体的SEM图如图1所示,TEM图如图2(a)和图2(b)所示,通过SEM图、TEM图以及建立晶体模型分析所制备的二十面星状结构金纳米晶体表面所暴露的原子排列规律,可从理论上验证及确定其晶体结构为二十面体的每一个面上外延生长一个三角锥,其表面密勒指数由{331}及邻近的{hhl}高指数晶面构成。
实施例2
本实施例的二十面星状结构金纳米晶体通过如下步骤制备得到:
(1)制备氯化胆碱-脲基低共熔溶剂:将氯化胆碱和脲按摩尔比为1:2添加到圆底烧瓶中并密封,置于80℃甘油浴中并磁力搅拌至无色液体,置于真空干燥箱中60℃下干燥12h,备用;
(2)配制镀金液:称取1.24g的氯金酸溶于100mL步骤(1)所制备的低共熔溶剂中,配制成含有30mM氯金酸的氯化胆碱-脲基低共熔溶剂溶液,置于25℃的恒温箱中陈化5个月至无色,备用;
(3)玻碳电极预处理:使用玻碳电极(Φ=6mm)为工作电极,在每次电沉积前分别使用1.0μm和0.3μm粒径的氧化铝研磨粉对玻碳电极进行抛光处理,研磨时间5min;然后在超纯水浴中超声清洗,清洗4次,除去电极表面的氧化铝研磨粉,以获得新鲜的玻碳工作电极表面,备用;
(4)制备星状结构金纳米晶体:将步骤(3)处理过的工作电极置于盛有10mL步骤(2)配制的镀液的三电极电解池中,参比电极和对电极分别为铂丝电极和铂片电极,运用双电位阶跃法调节成核电位(EN)为-0.95V、成核时间(tN)为0.2s、生长电位(EG)为-0.53V和生长时间(tG)为300s,沉积温度80℃,得二十面星状结构金纳米晶体。
该实施例所制备的二十面星状结构金纳米晶体的TEM图见图2(c)。
实施例3
(1)制备氯化胆碱-脲基低共熔溶剂:将氯化胆碱和脲按摩尔比为1:3添加到圆底烧瓶中并密封,置于70℃甘油浴中并磁力搅拌至无色液体,置于真空干燥箱中60℃下干燥12h,备用;
(2)配制镀金液:称取0.82g的氯金酸溶于200mL步骤(1)所制备的低共熔溶剂中,配制成含有10mM氯金酸的氯化胆碱-脲基低共熔溶剂溶液,置于30℃的恒温箱中陈化4个月至无色,备用;
(3)玻碳电极预处理:使用玻碳电极(Φ=6mm)为工作电极,在每次电沉积前分别使用1.0μm和0.3μm粒径的氧化铝研磨粉对玻碳电极进行抛光处理,研磨时间4min;然后在超纯水浴中超声清洗,清洗6次,除去电极表面的氧化铝研磨粉,以获得新鲜的玻碳工作电极表面,备用;
(4)制备星状结构金纳米晶体:将步骤(3)处理过的工作电极置于盛有10mL步骤(2)配制的镀液的三电极电解池中,参比电极和对电极分别为铂丝电极和铂片电极,运用双电位阶跃法调节成核电位(EN)为-0.1V、成核时间(tN)为0.3s、生长电位(EG)为-0.57V和生长时间(tG)为900s,沉积温度70℃,得二十面星状结构金纳米晶体。
该实施例所制备的二十面星状结构金纳米晶体的TEM图见图2(d)。
实施例4
将实施例1制得的二十面星状结构金纳米晶体催化剂电极置于盛有50mL氮气饱和的0.1mM HCl支持电解质的H型电解池中,阴极和阳极使用211型Nafion膜隔离,参比电极和对电极分别为饱和氢电极和石墨片电极。在每次电催化氮还原反应前,阴极槽中的支持电解质溶液预先通入99.999%氮气1h,氮气流速为50cm3 min-1,并在电催化氮还原反应时继续保持该流速通入阴极槽,以获得氮气饱和的0.1mM HCl支持电解质溶液。
氮还原反应电位分别设在-0.3V、-0.4V、-0.5V、-0.6V和-0.7V下进行,反应时间为2h,温度为25℃,压强为1atm,并记录氮还原反应在各电位下的i-t曲线,如图3所示。
运用靛酚蓝比色法,使用紫外-可见光谱法进行测试各电位下氮还原反应产物,具体方法如下:取2mL氮还原反应2h后的反应溶液,并向其中添加2mL含5%wt水杨酸和5%wt柠檬酸钠的1M氢氧化钠溶液,再添加1mL 0.05M的次氯酸钠,最后添加0.2mL1%wt硝普钠,混匀,静置1h后使用紫外分光光度计进行测试,测试结果如图4和图5所示。经比较,本发明实施例1所制备二十面星状结构金纳米晶体在-0.4V下表现出高的产氨速率,高达49.3μgh-1cm-2,法拉第效率高达28%。
对比例
选用球状的商业金粉(CAS:7440-57-5,0.5~0.8μm)作为催化剂,SEM图如图6所示。其作为催化剂电极的制备方法如下:(1)称取3.5mg球状商业金粉催化剂及量取50μL5wt%的Nafion溶液添加到盛有600μL无水乙醇的试剂瓶中,并置于25℃恒温水浴中超声分散20min,制得含有5.83μgμL-1的球状商业金粉催化剂/无水乙醇浆液;(2)量取步骤(1)所制备的15μL球状商业金粉催化剂/无水乙醇浆液悬滴到已预处理的玻碳电极(Φ=6mm)表面,自然晾干,备用。
比较本发明实施例1制得的二十面星状结构金纳米晶体与对比例的球状商业金粉催化剂在-0.4V下的电催化氮还原合成氨性能。测试步骤与实施例4相同,测试结果如图7和图8所示。可以看出,本发明所制备二十面星状结构金纳米晶体在-0.4V下的电催化氮还原合成氨性能(产氨速率:49.3μg h-1cm-2,法拉第效率:28%)大大高于球状商业金粉催化剂的电催化氮还原合成氨性能(产氨速率:14.2μg h-1cm-2,法拉第效率:7.8%)。
Claims (7)
1.一种星状结构金纳米晶体的制备方法,其特征在于,包括如下步骤:
(1)制备低共熔溶剂:将氯化胆碱和脲混合于烧杯中,密封,60~80℃搅拌至无色液体,制得氯化胆碱-脲基低共熔溶剂;
(2)配制镀金液:将氯金酸溶于步骤(1)所制备的低共熔溶剂中,60~80℃配制成镀金液,25~30℃陈化至无色,所述陈化时间为3个月以上;
(3)玻碳电极预处理:使用玻碳电极为工作电极,使用氧化铝研磨粉对玻碳电极进行抛光处理,超声清洗后备用;
(4)制备星状结构金纳米晶体:将步骤(3)的工作电极置于盛有步骤(2)镀金液的三电极电解池,参比电极为铂丝电极,对电极为铂片电极,运用双电位阶跃法调节成核电位、成核时间、生长电位和生长时间,沉积温度60~80℃,制得星状结构金纳米晶体,其中,所述成核电位为-0.95~-0.1V,成核时间为0.2~0.3s,所述生长电位为-0.53~-0.57V,生长时间为300~900s。
2.根据权利要求1所述的星状结构金纳米晶体的制备方法,其特征在于:步骤(1)中,氯化胆碱和脲的摩尔比为2:3~1:3。
3.根据权利要求1所述的星状结构金纳米晶体的制备方法,其特征在于:步骤(2)中,镀液中氯金酸的浓度为10~30mM。
4.根据权利要求1所述的星状结构金纳米晶体的制备方法,其特征在于:步骤(3)中,氧化铝研磨粉粒径为0.3~5.0μm,研磨时间3~5min,超声清洗次数4~6次。
5.权利要求1所制备的星状结构金纳米晶体,其特征在于:其晶体结构为二十面体的每一个面上外延生长一个三角锥,其表面密勒指数由{331}及邻近的{hhl}高指数晶面构成。
6.根据权利要求5所述的星状结构金纳米晶体,其特征在于:所述金纳米晶体的粒径为300~500nm。
7.权利要求1所制备的星状结构金纳米晶体作为电化学固氮催化剂在合成氨领域的应用,所述星状结构金纳米晶体催化剂在氮还原反应电位-0.4V下产氨速率达49.3μgh-1cm-2,法拉第效率达28%。
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