CN115323425A - 空心钌铜合金纳米电催化材料及其制备方法 - Google Patents
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- XCEAGAJKBRACAD-UHFFFAOYSA-N [Cu].[Ru] Chemical compound [Cu].[Ru] XCEAGAJKBRACAD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 63
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 150000001868 cobalt Chemical class 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims description 30
- 239000000084 colloidal system Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 17
- 239000001509 sodium citrate Substances 0.000 claims description 17
- 150000001879 copper Chemical class 0.000 claims description 15
- 150000003303 ruthenium Chemical class 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000010949 copper Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 229910052697 platinum Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- -1 ruthenium oxide ions Chemical class 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
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- 229920000557 Nafion® Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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Abstract
本发明公开了一种空心钌铜合金纳米电催化材料,用于电解水析氢反应;所述空心钌铜合金纳米电催化材料包括有多个空心纳米颗粒,所述空心纳米颗粒呈球状,所述空心纳米颗粒的壳层结构为钌铜合金。所述空心纳米颗粒的直径为15至50nm。本发明先将钴盐中的钴离子还原形成钴单质纳米颗粒作为模板,再通过钌、铜金属离子与钴之间的置换反应合成钌铜合金纳米电催化材料。本发明公开的空心钌铜合金纳米催化材料中的纳米颗粒呈空心球状,增加了材料的层次结构和比表面积,提供了更多的活性位点,提升了材料的催化性能;本发明公开的制备方法的操作温度为室温,合成工艺简单,原料及操作成本低廉,便于生产制造。
Description
技术领域
本发明涉及材料科学和电催化技术领域,尤其涉及一种空心钌铜合金纳米电催化材料及其制备方法。
背景技术
凭借高热值、可再生、二氧化碳零排放等特点,氢气逐渐成为公认的极具发展潜力的理想清洁能源。目前,工业上主要采用的制氢方法包括:甲烷重整、醇裂解和煤炭气化,但是这些方法的碳排放量都很高,也不具备可持续性。相比较而言,可持续生产高纯度氢气和氧气的电催化分解水技术具有极大的应用优势,是环保、高效制氢的有效途径。析氢反应(HER)和析氧反应(OER)是电解水技术的核心组成,而其中高效的催化剂是突破反应动力学惰性引起的过高电位这一瓶颈的关键所在。铂基贵金属材料被认为是最先进的析氢反应催化剂,然而其昂贵的价格和有限的存储量大大限制了氢能源的商业化应用。因此,开发经济、高效且稳定的新型电解水催化剂对实现高效电解水制氢至关重要。
发明内容
为了解决现有技术中,铂基贵金属析氢反应催化剂材料价格昂贵,成本高昂的问题,本发明提出一种价格低廉,用以代替铂基贵金属析氢反应催化剂的空心钌铜合金纳米电催化材料,本发明还公开了所述电催化剂材料的制备方法。
本发明是通过以下技术方案实现的:
空心钌铜合金纳米电催化材料,用于电解水析氢反应;
所述空心钌铜合金纳米电催化材料包括有多个空心纳米颗粒,所述空心纳米颗粒呈球状,所述空心纳米颗粒的壳层为钌铜合金。
进一步的,所述空心纳米颗粒的直径为15至50nm。
空心钌铜合金纳米电催化材料制备方法,包括:
将钴盐与柠檬酸钠溶于水中,在氮气保护下搅拌至完全溶解且混合均匀;
将硼氢化钠溶液加入至钴盐与柠檬酸钠溶液中,充分反应生成纳米钴胶体;
将钌盐溶液和铜盐溶液混合均匀后滴加至纳米钴胶体中,搅拌至充分反应得到纳米钌铜胶体;
离心纳米钌铜胶体获得沉淀,并用无水乙醇清洗沉淀,获取如上述的空心钌铜合金纳米电催化材料。
进一步的,所述将钴盐与柠檬酸钠溶于水中具体包括:
所述钴盐为氯化钴,所述钴盐的质量为9-18mg;
所述柠檬酸钠的质量为20-40mg;
所述水为除气水,体积为50mL。
进一步的,所述钴盐与所述柠檬酸钠的物质的量的比为0.45:1。
进一步的,所述硼氢化钠溶液为冰水溶液。
进一步的,所述钌盐溶液与所述铜盐溶液混合前的浓度相同,且范围均为5-10mmol/L;
所述钌盐溶液混合前的体积范围为0.8-6.4mL;
所述铜盐溶液混合前的体积范围为0.8-6.4mL。
进一步的,所述钌盐溶液与所述铜盐溶液混合前的浓度为5mmol/L;所述钌盐溶液的体积为1.6mL,所述铜盐溶液的体积为6.4mL。
进一步的,所述钌盐溶液与所述铜盐溶液混合前的浓度为10mmol/L;所述钌盐溶液的体积为0.8mL,所述铜盐溶液的浓度为3.2mL。
进一步的,所述离心纳米钌铜胶体获得沉淀,并用无水乙醇清洗沉淀具体包括:
离心纳米钌铜胶体,移出上层清液保留沉淀;
向沉淀中加入无水乙醇,并使沉淀分散在无水乙醇内;
重复离心和无水乙醇清洗,至无水乙醇清洗空心钌铜合金纳米颗粒三次。
本发明的有益效果在于:
本发明公开的空心钌铜合金纳米催化材料中的纳米颗粒呈空心球状,空心结构形貌增加了材料的层次结构和比表面积,提供了更多的活性位点,提升了材料的催化性能;同时,本发明中所用的钌与铜的市场价格低廉,相较于铂,可以有效降低催化材料的生产制作成本;此外,本发明采用的将金属合金化的方法,有效调节催化材料表面的电子和结构性质,钌铜间的协同效应提升了材料的催化性能;
本发明公开的制备方法的操作温度为室温,实验操作简单,易于重复,原料及操作成本低,便于生产制造。
附图说明
图1是本发明以实施例1制备获取的空心钌铜合金纳米电催化材料的透射电镜图;
图2是本发明以实施例2制备获取的空心钌铜合金纳米电催化材料的透射电镜图;
图3是本发明分别以实施例1和实施例2制备得到的空心钌铜合金纳米电催化材料的析氢反应极化曲线;
图4是图3中两例实施例在电流密度为10mA·cm-2和50mA·cm-2时的过电位。
具体实施方式
为使本发明的目的、技术方案及效果更加清楚、明确,以下参照附图并举实施例对本发明做进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
本发明公开了一种空心钌铜合金纳米电催化材料,应用于电解水的析氢反应。空心钌铜合金纳米电催化材料由多个空心纳米颗粒组成。请参考图1和图2,空心纳米颗粒呈球状,空心纳米颗粒的壳层为钌铜合金。进一步的,空心纳米颗粒的直径范围15至50nm。
本发明公开的空心钌铜合金纳米电催化材料作为铂的低价替代品,金属钌(市场价格仅为铂价格的4%)具有与铂相似的氢键强度(65kcal/mol),因此氢气解吸能垒低,HER催化性能优异,在电解水析氢领域具有广阔的发展前景,本发明公开的空心钌铜合金纳米电催化材料,旨在提供一种廉价的、催化性能有望替代铂的电催化剂。
本发明还公开了制备上述空心钌铜合金纳米电催化材料的制备方法,制备方法包括如下步骤:
步骤一:将9-18mg的钴盐与20-40mg的柠檬酸钠溶于50mL的除气水中,在氮气保护下搅拌至完全溶解且均匀混合,搅拌转速为200-400rpm,搅拌时间30-60min。在本发明的一个可实现的实施例中,以氯化钴为例,氯化钴与柠檬酸钠的物质的量比为0.45:1,所述柠檬酸钠的使用量为40mg,所述氯化钴的使用量为18mg。氮气主要起到保护作用,也可以选择用氩气等化学性质呈惰性的气体,氮气或惰性气体通入反应环境的目的,主要是排除反应环境外的氧气和水蒸气,避免影响后续钴纳米颗粒的合成,同时避免氧化钌离子,干扰最终合金产物的形成。
步骤二:将浓度为1mg/mL,体积为40mL的硼氢化钠溶液加入到钴盐与柠檬酸钠溶液中,充分反应生成钴纳米颗粒。硼氢化钠具有很强的还原性,在常温下会与水反应缓慢生成氢气,因而,本发明中的硼氢化钠溶液为冰水溶液,用于降低硼氢化钠与水反应的速率,保证其还原性,使其在加入到混合液中时,能将钴盐还原成钴单质。
钴离子被还原成单质后,在液体环境中以钴纳米颗粒形式存在,钴纳米颗粒的直径在1-100nm之间,钴与液体环境形成纳米钴胶体形式的分散系。
步骤三:将钌盐溶液和铜盐溶液混合均匀后滴加至纳米钴胶体中,充分反应得到纳米钌铜胶体。钌离子与铜离子氧化钴单质,使钴再次以离子的形式分散在液体环境中,钌离子和铜离子则获得电子后逐渐附着在钴颗粒的外围,直至形成以钌铜合金为壳,内部中空的多个空心钌铜合金纳米颗粒,形成的钌铜合金纳米颗粒的直径范围同样在1-100nm之间,因而在反应完成后,合金颗粒与液体环境形成纳米钌铜胶体形式的分散系。
本发明的步骤三有两种实施方式,以下将分别进行介绍:
实施例1,将1.6mL浓度为5mmol/L的氯化钌和6.4mL浓度为5mmol/L的氯化铜混合均匀后滴加到纳米钴胶体中,搅拌60min,得到纳米钌铜胶体;
实施例2,将0.8mL浓度为10mmol/L的氯化钌和3.2mL浓度为10mmol/L的氯化铜混合均匀后滴加到纳米钴胶体中,搅拌60min,得到纳米钌铜胶体。
在上述的实施方式中,氯化钌和氯化铜的总物质的量不变,只是更改了溶液的浓度及使用体积。
在上述的反应中,钴单质纳米颗粒为反应模板,溶液中的钌离子与铜离子与钴单质发生置换反应,钌和铜逐渐在钴纳米颗粒外形成壳层结构,颗粒内部的钴单质逐渐释放至溶液中,最后形成钌铜合金纳米颗粒。
步骤四:
以10000转/分钟离心纳米钌铜胶体10分钟,移出上层清液后保留沉淀;
向沉淀中加入无水乙醇,并超声震荡使沉淀分散在无水乙醇内,以实现清洗沉淀的目的;
重复执行“离心-移出上层清液-无水乙醇清洗”的操作,直至沉淀第三次分散在无水乙醇内,此时无水乙醇内即分散有获取的空心钌铜合金纳米电催化材料。
经过上述制备后,运用透射电镜观察制备的空心钌铜合金纳米电催化材料的结构,本发明公开的制备方法中,步骤三有两种实施方式,最终获取材料的透射电镜图分别如图1和图2所示。其中,图1的纳米颗粒直径分布在20-40nm范围,图2的纳米颗粒直径分布范围为15-35nm。
制备的电催化材料需验证其电催化性能,本发明公开的验证方法是通过三电极体系测试系统实现的:其中参比电极采用饱和甘汞电极,对电极为碳棒,工作电极为涂布在玻碳电极表面的空心钌铜合金纳米电催化材料,玻碳电极的直径为3mm,工作电极的制备方法为:
将一定质量的空心钌铜合金纳米电催化材料分散在3mL的无水乙醇中,用移液枪分次量取共10μL滴在玻碳电极表面,至自然干燥;随后,用移液枪量取1μL Nafion(5%)溶液滴在玻碳电极表面,至自然干燥。之后进行LSV测试,测试在0.5M的硫酸溶液中进行,其中,线性扫描速度为5mV/s。
图3为本发明中用实施例1和实施例2两种方法制备的空心钌铜合金纳米电催化材料各自的LSV曲线,从图中可以看出,两种直径的空心钌铜合金纳米电催化材料均表现出了良好的HER析氢性能,其中可见,如步骤三以实施例2操作制作的空心钌铜合金纳米电催化材料催化性能更好。图4列举了图3中实施例1和实施例2驱动10mA·cm-2和50mA·cm-2所需要的电势分别为252.0mV、307.5mV和201.8mV、344.3mV。
在本发明其他的可实现的实施例中,本发明公开的所述空心钌铜合金纳米电催化材料还被用于实时监测催化反应过程,操作人员利用铜本身的SERS增强性能对催化过程中钌铜表面物种的拉曼信号加以收集,通过分析其变化,了解其反应过程或推知其反应机理。本发明公开的空心钌铜合金纳米电催化材料中的纳米颗粒呈空心球状,空心结构形貌增加了材料的层次结构和比表面积,提供了更多的活性位点,提高了材料的催化效率;同时,本发明中所用的钌与铜的市场价格低廉,相较于铂,可以有效降低催化材料的生产制作成本;此外,本发明中采用的将金属合金化的方法,能有效调节催化材料表面的电子和结构性质,钌铜间的协同效应有效提升材料的催化性能;
本发明公开的制备方法的操作温度为室温,实验操作简单,易于重复,原料及操作成本低,便于生产制造。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (10)
1.空心钌铜合金纳米电催化材料,其特征在于,用于电解水析氢反应;
所述空心钌铜合金纳米电催化材料包括有多个空心纳米颗粒,所述空心纳米颗粒呈球状,所述空心纳米颗粒的壳层为钌铜合金。
2.根据权利要求1所述的空心钌铜合金纳米电催化材料,其特征在于,所述空心纳米颗粒的直径为15-50nm。
3.空心钌铜合金纳米电催化材料制备方法,其特征在于,包括:
将钴盐与柠檬酸钠溶于水中,在氮气保护下搅拌至完全溶解且混合均匀;
将硼氢化钠溶液加入至钴盐与柠檬酸钠溶液中,充分反应生成纳米钴胶体;
将钌盐溶液和铜盐溶液混合均匀后滴加至纳米钴胶体中,搅拌至充分反应得到纳米钌铜胶体;
离心纳米钌铜胶体获得沉淀,并用无水乙醇清洗沉淀,获取如权利要求1或2所述的空心钌铜合金纳米电催化材料。
4.根据权利要求3所述的钌铜合金纳米电催化材料制备方法,其特征在于,所述将钴盐与柠檬酸钠溶于水中具体包括:
所述钴盐为氯化钴,所述钴盐的质量为9-18mg;
所述柠檬酸钠的质量为20-40mg;
所述水为除气水,体积为50mL。
5.根据权利要求3所述的空心钌铜合金纳米电催化材料制备方法,其特征在于,所述钴盐与所述柠檬酸钠的物质的量的比为0.45:1。
6.根据权利要求3所述的空心钌铜合金纳米电催化材料制备方法,其特征在于,所述硼氢化钠溶液为冰水溶液。
7.根据权利要求3所述的空心钌铜合金纳米电催化材料制备方法,其特征在于,所述钌盐溶液与所述铜盐溶液混合前的浓度相同,且范围均为5-10mmol/L;
所述钌盐溶液混合前的体积范围为0.8-6.4mL;
所述铜盐溶液混合前的体积范围为0.8-6.4mL。
8.根据权利要求7所述的空心钌铜合金纳米电催化材料制备方法,其特征在于,所述钌盐溶液与所述铜盐溶液混合前的浓度为5mmol/L;所述钌盐溶液的体积为1.6mL,所述铜盐溶液的体积为6.4mL。
9.根据权利要求7所述的空心钌铜合金纳米电催化材料制备方法,其特征在于,所述钌盐溶液与所述铜盐溶液混合前的浓度为10mmol/L;所述钌盐溶液的体积为0.8mL,所述铜盐溶液的浓度为3.2mL。
10.根据权利要求3所述的空心钌铜合金纳米电催化材料制备方法,其特征在于,所述离心纳米钌铜胶体获得沉淀,并用无水乙醇清洗沉淀具体包括:
离心纳米钌铜胶体,移出上层清液保留沉淀;
向沉淀中加入无水乙醇,并使沉淀分散在无水乙醇内;
重复离心和无水乙醇清洗,至无水乙醇清洗空心钌铜合金纳米颗粒三次。
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