CN111420676B - 一种无机有机杂化金属超粒子及其制备方法和应用 - Google Patents
一种无机有机杂化金属超粒子及其制备方法和应用 Download PDFInfo
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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Abstract
本发明提供了一种无机有机杂化金属超粒子及其制备方法和应用。该制备方法包括:向聚合物水溶液中加入金属离子溶液,加入还原剂,在60℃‑100℃下搅拌30min‑480min;加入沉淀剂,沉淀后离心,将离心得到的固体分散到水溶液中,得到无机有机杂化金属超粒子。本发明的无机有机杂化金属超粒子经过处理后可以用于催化电解水反应,并具有较好的催化活性和稳定性。
Description
技术领域
本发明涉及一种催化剂,尤其涉及一种电催化分解水的催化剂,属于催化剂制备技术领域。
背景技术
电解水制氢是一种清洁、高效、可持续的新能源技术,是解决当前能源问题和环境问题的有效途径。但在动力学上,水分解反应的进行十分困难,极大地限制了其在工业中的应用。使用催化剂促进电解水反应可以有效提高产氢效率,降低电解水所需电压。因此,开发出一种高效、稳定的电解水催化剂已成为当前科学研究的焦点之一。
目前,已报道的全解水电催化剂可分为贵金属基催化剂,如β-Ni2P2O7/Pt(ACSAppl.Mater.Interfaces 2019,11,4969-4982)、Pt@DNA–GC(ACS Catal.2016,67,4660-4672);和非贵金属催化剂,如3D-OMNiSA(ACS Catal.2016,6,1446-1450)、Ni3N-VN/NF(Adv.Mater.2019,1901174)等。这些催化剂在降低电解水过电势方面已经取得了极大的进展,但他们的合成方法都比较繁琐,困难,而且反应稳定性仍有待提高。
因此,开发一种合成方法简单,反应过程稳定的电解水催化剂仍然本领域亟待解决的一个问题。
发明内容
本发明的一个目的在于提供催化活性高、稳定性好的电催化全解水催化剂。
本发明的另一个目的在于提供上述电催化全解水催化剂的制备方法。
为了实现上述目的,本发明提供了一种无机有机杂化金属超粒子的制备方法,该制备方法包括以下步骤:
向浓度为0.0045mmol/L-150mmol/L的聚合物水溶液中加入浓度为0.01mmol/L-50mmol/L的金属离子溶液,加入还原剂,在60℃-100℃下搅拌30min-480min,得到混合溶液;其中,聚合物与金属离子的摩尔比为1:250-600000:1;
向混合溶液中加入沉淀剂,沉淀后离心,将离心得到的固体分散到水中,得到无机有机杂化金属超粒子。
本发明的无机有机杂化金属超粒子的制备方法通过控制金属离子与聚合物的加入比例,制备尺寸可控的无机有机杂化金属超粒子,聚合物添加量越多,无机有机杂化金属超粒子的粒径越小,构成单个超粒子的纳米簇越少;通过调节含不同杂原子聚合物的种类,实现调节碳化超粒子的电子结构,获得较优的电催化水分解性能。
本发明的无机有机杂化金属超粒子的制备方法,包括制备超粒子的步骤。其是向水溶性聚合物水溶液中加入一定浓度的金属离子作为前驱体,待分散均匀后,向溶液中加入还原剂,加热一定时间,一步制备出超粒子。
在本发明的制备方法中,采用水溶性的聚合物作为稳定剂,使超粒子的粒径均匀。在本发明的一具体实施方式中,聚合物水溶液中采用的聚合物可以为聚丙烯酸甲酯、聚丙烯酸、聚乙烯亚胺、聚乙二醇或聚烯丙基胺盐酸盐。
在本发明的一具体实施方式中,聚合物的分子量为1800g/mol-30000g/mol。
在本发明的一具体实施方式中,聚合物水溶液的浓度可以为0.05mmol/L-50mmol/L,进一步优选为0.1mmol/L-10mmol/L。
在本发明的一具体实施方式中,金属离子溶液中采用的金属离子可以为Au3+、Pt4 +、Ag+或Cu2+。
在本发明的一具体实施方式中,金属离子溶液可以为HAuCl4水溶液、H2PtCl6水溶液、AgNO3水溶液、CH3COOAg水溶液、AgF水溶液、Ag2SO4水溶液、AgClO4水溶液、CuCl2水溶液、CuNO3水溶液、CuSO4水溶液或CH3COOCu水溶液。
在本发明的一具体实施方式中,金属离子溶液的浓度为0.01mmol/L-30mmol/L;进一步优选为0.1mmol/L-30mmol/L。
在本发明的一具体实施方式中,采用的还原剂可以为硼氢化钠、水合肼、柠檬酸钠或抗坏血酸;优选地,还原剂与金属离子的摩尔比可以为1-10:1。
本发明的无机有机杂化金属超粒子的制备方法,包括制备聚合物包覆的金属超粒子的步骤。其是采用沉淀剂沉淀上述超粒子得到的。
在本发明的一具体实施方式中,采用的沉淀剂为丙酮;优选地,沉淀剂的添加体积为混合溶液的体积的2倍-10倍。
本发明还提供了一种无机有机杂化金属超粒子,该无机有机杂化金属超粒子是由本发明的无机有机杂化金属超粒子的制备方法制备得到的。该无机有机杂化金属超粒子的粒径均匀,该无机有机杂化金属超粒子的平均粒径为30nm-150nm(55nm),由数20个-50个平均粒径为2nm-5nm(4nm)金属纳米簇通过有机聚合物层包覆、桥连而成。
本发明还提供了一种电催化全解水催化剂,该催化剂是通过以下步骤制备得到的:
将经过酸洗处理的泡沫镍,放入本发明的上述无机有机杂化金属超粒子的分散液中浸渍24h-48h;
将浸渍于超粒子分散液的泡沫镍取出后,在60℃-80℃下烘干4h-8h,在氩气保护下,300℃-600℃下焙烧2h-3h,得到电催化全解水催化剂;该催化剂由碳化后的杂化金属超粒子负载于泡沫镍表面所构成,碳化后的超粒子平均粒径为30nm-150nm,由20个-50个平均粒径为2nm-5nm的金属纳米簇通过有机聚合物层包覆、桥连而成。
本发明的电催化剂全解水催化剂可以用电催化全解水。
本发明的无机有机杂化金属超粒子经过处理后,可以用于电催化全解水。制备的超粒子因具有石榴状结构,且经过高温处理后,构成超粒子的金属纳米簇,其表面起到稳定作用的聚合物被碳化,使金属纳米簇被碳材料所包覆,能够高度地将金属纳米簇分散在碳材料中,提高金属元素的利用效率。此外,碳材料中的杂原子(硫、氮、磷)可以调变金属元素的电子结构,优化材料的氢吸附能,同时,碳材料中的杂原子也是良好的水吸附位点。另外,包裹金属纳米簇的碳材料还可以有效地防止金属纳米簇团聚、中毒,有效提高材料的电催化活性和稳定性。
本发明的无机有机杂化金属超粒子的制备方法的环境污染小,产物纯度高,方法简单,容易操作,重复性好,适合大量生产。
由本发明的制备方法得到的无机有机杂化金属超粒子经过处理后,具有优异的电催化析氢反应活性和析氧反活性,并具有优良的稳定性,是一种性能优异的电催化全解水催化剂。
本发明的电催化全解水催化剂电催化全解水时,具有优异的催化性能。
附图说明
图1为实施例1的Au超粒子的透射电子显微镜图。
图2为实施例2的电催化全解水催化剂的电催化析氢线性扫描伏安法曲线。
图3为实施例2的电催化全解水催化剂的电催化析氧循环伏安法曲线。
图4为实施例3的电催化全解水催化剂的电催化稳定性i-t曲线。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解,现对本发明的技术方案进行以下详细说明,但不能理解为对本发明的可实施范围的限定。
实施例1
本实施例提供了一种电催化全解水催化剂,其是通过以下步骤制备得到的:
称取0.035g的聚乙烯亚胺作为稳定剂溶解在10mL水中,依次加入0.5mL浓度为50mmol/L的HAuCl4溶液,0.05g的柠檬酸钠,搅拌10min后,在70℃下加热5h后,将反应后的溶液以丙酮为沉淀剂洗涤后,以离心的方式收集沉淀,并将沉淀分散在5mL水中,以上操作重复三遍,所得深黄色溶液即为Au超粒子。
将经过酸洗处理的泡沫镍裁剪为1cm×2cm的长方形,放入上述Au超粒子水溶液中浸渍24h,然后在80℃下烘干4h,将干燥的泡沫镍和金属超粒子复合物在氩气保护下,在500℃焙烧3h,得到电催化全解水催化剂。
实施例2
本实施例提供了一种电催化全解水催化剂,其是通过以下步骤制备得到的:
称取0.015g的聚丙烯酸作为稳定剂溶解在5mL水中,向溶液中分别加入0.25mL的浓度为40mmol/L的氯铂酸溶液,500μL一水合肼,在80℃下加热4h后,将反应后的溶液以丙酮为沉淀剂洗涤后,以离心的方式收集沉淀,并将沉淀分散在5mL水中,以上操作重复三遍,所得淡黑色溶液即为Pt超粒子。
将经过酸洗处理的泡沫镍裁剪为1cm×2cm的长方形,放入上述Pt超粒子水溶液中浸渍24h,然后在80℃下烘干4h,将干燥的泡沫镍和金属超粒子复合物在氩气保护下,在500℃焙烧3h,得到电催化全解水催化剂(以泡沫镍负载碳化后的无机有机杂化金属超粒子),作为待测样品。
所制得的电催化全解水催化剂具有良好的电催化水分解活性(图2和图3)。
在进行电解水析氢反应测试时,使用的电化学工作站型号为上海辰华CHI760e,电解质溶液为0.5mol/L的硫酸溶液,参比电极为饱和甘汞电极,对电极为石墨电极,工作电极为待测样品(1cm×2cm)。将各电极与电化学工作站连接并伸入电解液中,工作电极伸入液面的深度为0.5cm。使用线性扫描伏安法进行测试,采用仪器自动补偿电阻,扫描范围为0V至-1V,扫描速率为5mV/s。
在进行电解水析氧反应测试时,使用的电化学工作站型号为上海辰华CHI760e,电解质溶液为1mol/L的氢氧化钾溶液,参比电极为氧化汞电极,对电极为铂丝电极,工作电极为待测样品(1cm×2cm),将各电极与电化学工作站连接并伸入电解液中,工作电极伸入液面的深度为0.5cm。使用循环伏安法进行测试,扫描范围为0V至1V,扫描速率为5mV/s。
由图2可以看出,电流达到10mA/cm2时所需要的过电势,杂化Pt超粒子为134.0mV,商业20%铂碳催化剂(麦克林品牌CAS号:7440-06-4)为206.2mV,表明杂化Pt超粒子具有优于商业铂碳催化剂的析氢活性。
由图3可以看出,在电流达到10mA/cm2时所需要的过电势,杂化Pt超粒子和商业20%铂碳催化剂(麦克林品牌CAS号:7440-06-4)都为1.54V,表明杂化Pt超粒子的析氧活性与商业铂碳催化剂相当。
实施例3
本实施例提供了一种电催化全解水催化剂,其是通过以下步骤制备得到的:
称取0.025g的聚烯丙基胺盐酸盐作为稳定剂溶解在5mL水中,向溶液中分别加入0.25mL浓度为40mmol/L的硝酸银溶液,0.03g硼氢化钠,在80℃下加热4h后,将反应后的溶液以丙酮为沉淀剂洗涤后,以离心的方式收集沉淀,并将沉淀分散在5mL水中,以上操作重复三遍,所得淡黑色溶液即为Ag超粒子。
将经过酸洗处理的泡沫镍裁剪为1cm×2cm的长方形,放入Ag超粒子水溶液中浸渍24h,然后在80℃下烘干4h,将干燥的泡沫镍和金属超粒子复合物在氩气保护下,在500℃焙烧3h,得到电催化全解水催化剂(待测样品)。
所制得的电催化全解水催化剂具有良好的电催化稳定性(图4)。
在进行电解水稳定性测试时,使用的电化学工作站型号为上海辰华CHI760e,电解质溶液为0.5mol/L的硫酸溶液,参比电极为饱和甘汞电极,对电极为石墨电极,工作电极为待测样品(1cm×2cm)。将各电极与电化学工作站连接并伸入电解液中,工作电极伸入液面的深度为0.5cm。使用恒电压法进行测试,测试电压为-0.3V,测试时间为10h。
由图4可以看出,在10h的测试中,电流最终会稳定在4mA/cm2左右,电流密度没有发生明显的变化,说明杂化Ag超粒子具备良好的电催化稳定性。
Claims (8)
1.一种电催化全解水催化剂,该催化剂是通过以下步骤制备得到的:
将经过酸洗处理的泡沫镍,放入无机有机杂化金属超粒子的分散液中浸渍24h-48h;
在60℃-80℃下烘干4h-8h,在氩气保护下,300℃-600℃下焙烧2h-3h,得到电催化全解水催化剂;
其中,所述无机有机杂化金属超粒子按照以下步骤制备得到:
向浓度为0.0045mmol/L-150mmol/L的聚合物水溶液中加入浓度为0.01mmol/L-50mmol/L的金属离子溶液,加入还原剂,在60℃-100℃下搅拌30min-480min,得到混合溶液;其中,聚合物与金属离子的摩尔比为1:250-600000:1;所述聚合物水溶液中采用的聚合物为聚丙烯酸甲酯、聚丙烯酸、聚乙烯亚胺、聚乙二醇或聚烯丙基胺盐酸盐;
向混合溶液中加入沉淀剂,沉淀后离心,将离心得到的固体分散到水中,得到无机有机杂化金属超粒子;所述沉淀剂为丙酮;
该催化剂由杂化金属超粒子负载于泡沫镍表面所构成,杂化金属超粒子平均粒径为30nm-150nm,由20个-50个平均粒径为2nm-5nm的金属纳米簇通过有机聚合物层包覆、桥连而成。
2.根据权利要求1所述的电催化全解水催化剂,其中,聚合物的分子量为1800g/mol-30000g/mol。
3.根据权利要求1所述的电催化全解水催化剂,其中,所述金属离子溶液采用的金属离子为Au3+、Pt4+、Ag+或Cu2+。
4.根据权利要求3所述的电催化全解水催化剂,其中,所述金属离子溶液为HAuCl4水溶液、H2PtCl6水溶液、AgNO3水溶液、CH3COOAg水溶液、AgF水溶液、Ag2SO4水溶液、AgClO4水溶液、CuCl2水溶液、CuNO3水溶液、CuSO4水溶液或CH3COOCu水溶液。
5.根据权利要求1所述的电催化全解水催化剂,其中,所述还原剂为硼氢化钠、水合肼、柠檬酸钠或抗坏血酸。
6.根据权利要求1所述的电催化全解水催化剂,其中,所述还原剂与金属离子的摩尔比为1-10:1。
7.根据权利要求1所述的电催化全解水催化剂,其中,所述沉淀剂的添加体积为混合溶液的体积的2倍-10倍。
8.权利要求1-7任一项所述的电催化全解水催化剂的应用,该电催化全解水催化剂用于电催化全解水。
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CN107321385A (zh) * | 2017-06-28 | 2017-11-07 | 陕西师范大学 | 一种聚乙烯亚胺功能化的多枝状纳米三角形Pt催化剂的制备方法 |
CN110625135A (zh) * | 2019-10-14 | 2019-12-31 | 商丘师范学院 | 一种高效简易合成不同形貌Ru纳米晶的方法 |
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