CN107413360B - 一种碳纤维布负载CoMoP硼氢化钠水解制氢催化剂及其制备方法 - Google Patents
一种碳纤维布负载CoMoP硼氢化钠水解制氢催化剂及其制备方法 Download PDFInfo
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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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
本发明公开了一种碳纤维布负载CoMoP硼氢化钠水解制氢催化剂及其制备方法,该催化剂由载体碳纤维布表面负载钴、钼和磷制备而成;所述钴、钼和磷由氯化钴、钼酸钠、次亚磷酸钠的混合溶液通过单脉冲电镀法电镀于碳纤维布表面。本发明的催化剂的产氢效率高、分布致密、性能稳定,是一种非贵金属催化剂。本发明的催化剂中CoMoP通过单脉冲电镀法可以均匀分布在碳纤维布表面且结合致密,该催化剂在硼氢化钠水溶液中温度为60℃产氢速率可以高达11.40L/min·g。本发明催化剂的制备方法简单方便、原料成本低、可以进行大规模生产,可以为无人机、仿生鱼及其他便携式燃料电池电源和室外氢气球提供化学现场制氢技术。
Description
技术领域
本发明属于氢能及燃料电池技术领域,具体涉及一种碳纤维布负载CoMoP硼氢化钠水解制氢催化剂(CoMoP/CC催化剂)及其制备方法。
背景技术
氢能是一种清洁能源,作为低碳和零碳能源越来越受到消费者青睐。相对传统能源如石油、天然气、煤,氢能具有以下优点:(1)燃烧热值很高,燃烧同等质量的氢约为汽油的3倍,酒精的3.9倍,焦炭的4.5倍;(2)燃烧的产物是水,水是世界上最干净的能源,而且资源储量丰富。目前科学家们正在探索能够大量而廉价产氢的新技术,而利用水解产氢虽然操作方便,原材料易于获得,但是产同样的氢所消耗的成本实在太大,加上氢气存储技术要求颇高,因此,硼氢化钠水解制氢技术因运而生。NaBH4在常温下稳定,储存方法简单,NaBH4水解制氢被认为是一种安全、方便、实用性强的技术,其主要优点为理论储氢率高、氢气纯度高、反应启动快、易控制和安全。在催化剂存在下,硼氢化钠在碱性水溶液中可水解产生氢气和偏硼酸钠,反应如下:NaBH4+2H2O→4H2↑+NaBO2;25℃标准状态下,该反应过程的焓变为-217kJ,是放热反应。
如果没有催化剂,上述反应也能进行,其反应速度与溶液的pH值和温度有关,公式如下:lg t1/2=pH-(0.034T–1.92);式中t1/2是NaBH4半衰期(单位为分钟),T是绝对温度。当pH值为8时,即使在常温下,NaBH4溶液也会很快水解。在25℃和pH值为14的条件下,硼氢化钠溶液的半衰期为430天,这一特性足以满足现实生产需求。
利用硼氢化钠水解产氢是当前产氢技术中最为便携的一种,相比传统电解水制氢法优势颇多,但若要更快速更多量地获得氢气,还需要向产氢液中放入特制的催化剂。目前,现有技术中硼氢化钠水解制氢用催化剂以Pt、Ru贵金属及其合金颗粒催化剂为主,缺点是成本高、难回收、反应不易控制。
发明内容
发明目的:针对现有技术存在的问题,本发明提供一种碳纤维布负载CoMoP硼氢化钠水解制氢催化剂,即钴钼硼/碳纤维布(CoMoP/CC)催化剂,该催化剂是一种由非贵金属元素钴,钼,磷作为催化剂活性组分,碳纤维布作载体,通过单脉冲电镀法所制成的硼氢化钠水解产氢催化剂;是一种高效、低廉硼氢化钠水解制氢催化剂。
本发明还提供碳纤维布负载CoMoP硼氢化钠水解制氢催化剂的制备方法。
技术方案:为了实现上述目的,如本发明所述一种碳纤维布负载CoMoP硼氢化钠水解制氢催化剂,由载体碳纤维布表面负载钴、钼和磷制备而成;所述钴、钼和硼由氯化钴、钼酸钠、次亚磷酸钠的混合溶液通过单脉冲电镀法电镀于碳纤维布表面。
其中,所述碳纤维布为多孔分布状,面密度范围为200-300g/m2。
进一步地,所述氯化钴、钼酸钠、次亚磷酸钠的混合溶液中氯化钴的浓度10.4-15.6g/L(0.08-0.12mol/L)、钼酸钠的浓度18.1-30.2g/L(0.075-0.125mol/L)、次亚磷酸钠的浓度3.18-7.42g/L(0.03-0.07mol/L)。
本发明所述的碳纤维布负载CoMoP硼氢化钠水解制氢催化剂的制备方法,包括如下步骤:
(1)将碳纤维布样品浸在无水乙醇中,超声波振荡清洗;
(2)将步骤(1)乙醇浸泡过的碳纤维布用清洗后,然后浸在稀盐酸中超声振荡;
(3)将稀盐酸浸泡过的碳纤维布用去离子水超声振荡清洗,振荡清洗后进行干燥,称重并保存备用;
(4)配制氯化钴、钼酸钠、次亚磷酸钠混合溶液,以硼酸为缓冲剂、丁炔二醇为表面活性剂,通过稀硫酸调节pH;将步骤(3)得到碳纤维布浸泡在混合溶液中电镀,通过单脉冲电源进行电镀,电源正极连接铂电极,电源负极连接步骤(3)得到碳纤维布,通过单脉冲电镀法将钴、钼和磷电镀于碳纤维布表面;电镀后将碳纤维布取出,清洗,超声振荡,干燥即得碳纤维布负载CoMoP硼氢化钠水解制氢催化剂。
作为优选,步骤(2)所述稀盐酸浓度为0.01-0.02mol/L。
作为优选,步骤(4)所述混合液中硼酸浓度为20-40g/L。
作为优选,步骤(4)所述混合液中丁炔二醇浓度为0.05-0.1g/L。
作为优选,步骤(4)所述滴入稀硫酸调节pH值为4-5。
进一步地,步骤(4)所述单脉冲电镀法时间为10-40min。
进一步地,步骤(4)所述单脉冲电镀法的温度为10-40℃、电流密度为0.1-0.3A/cm2。
本发明采用了非贵金属元素Co、Mo、P,比贵金属Pt、Ru价格低廉,而贵重金属往往价格非常昂贵,因此用其作为催化剂成本太高,不利于生产发展,同时贵重金属催化剂所生成的副产物一般情况下无法循环使用,不利于市场推广应用。同时本发明采用单脉冲电镀法,有利于提高催化剂活性组分与载体间的结合力,防止催化剂在反应过程中脱落,可以大大提高催化剂的使用寿命,通过比较,本发明更具市场前景和技术优势。
本发明由于采用的碳纤维布表面多孔,力学性能较高,其面密度约为200-300g/m2;因此,制得的催化剂具有催化活性高,产氢性能稳定,非贵金属元素分布密致有序等特点。同时本发明采用单脉冲电镀法,有利于提高催化剂活性组分与载体间的结合力,防止催化剂在反应过程中脱落,可以大大提高催化剂的使用寿命,通过比较,本发明更具市场前景和技术优势。在试验中,发现改变电镀过程中一些重要条件如:电镀时间,镀液温度,镀液电导率(TDS),镀液的pH值,电镀电流密度,将会影响催化剂的催化活性。本发明进行了一系列的对比试验,并且筛选出来最优制备条件。因此,非贵金属元素的种类和其所加入的量也是影响催化剂整体性能的重要因素。
有益效果:与现有技术相比,本发明的制备的碳纤维布负载CoMoP硼氢化钠水解制氢催化剂的产氢效率高、分布致密、性能稳定,是一种高效、低廉硼氢化钠水解制氢非贵金属催化剂。本发明的催化剂中非贵金属元素CoMoP通过单脉冲电镀法可以均匀分布在碳纤维布表面且结合致密,该CoMoP/CC催化剂在硼氢化钠水溶液中温度为60℃的产氢速率可以高达11.40L/min·g。同时本发明的CoMoP/CC催化剂的制备方法简单方便,原料成本低、可以进行大规模生产。
附图说明
图1为本发明实施例1未进行单脉冲电镀的碳纤维布载体的SEM照片;
图2为本发明实施例1单脉冲电镀后制备的CoMoP/CC催化剂SEM照片;
图3为本发明试验例1中单脉冲电镀制备过程中氯化钴浓度对制备CoMoP/CC催化剂性能的影响;
图4为本发明试验例1中单脉冲电镀制备过程中钼酸钠浓度对制备CoMoP/CC催化剂性能的影响;
图5为本发明试验例1中单脉冲电镀制备过程中次亚磷酸钠浓度对制备CoMoP/CC催化剂性能的影响;
图6为本发明试验例3中反应温度对催化剂性能的影响规律。
具体实施方式
以下结合附图和实施例对本发明作进一步说明。
实施例1
(1)将面密度250g/m2碳纤维布样品浸在无水乙醇中,于25℃超声波振荡清洗10min,以充分清除碳纤维布表面的污渍;
(2)将步骤(1)乙醇浸泡过的碳纤维布用去离子水洗清后,然后浸在0.01mol/L稀盐酸中超声振荡5min,以达到去除表面杂质及氧化物;
(3)将稀盐酸浸泡过的碳纤维布用去离子水超声振荡清洗5min,振荡清洗后放入50℃干燥箱中烘干1-2h,称重并保存备用;
(4)配制(0.10mol/L)13g/L氯化钴、(0.10mol/L)24.2g/L钼酸钠、(0.05mol/L)5.3g/L次亚磷酸钠混合溶液,并加入30g/L硼酸为缓冲剂,0.075g/L丁炔二醇为表面活性剂;滴入稀硫酸调节pH值4.5;将步骤(3)得到碳纤维布浸泡在混合溶液中进行单脉冲电镀,电源正极连接铂电极,电源负极连接碳纤维布,时间为25min,温度为25℃,电流密度为0.2A/cm2;电镀后将碳纤维布取出,用无水乙醇清洗2-3次,浸入去离子水中超声振荡5min,最后50℃干燥箱中烘干30-45min。即得碳纤维布负载CoMoP硼氢化钠水解制氢催化剂。
实施例2
(1)将面密度200g/m2碳纤维布样品浸在无水乙醇中,于25℃超声波振荡清洗10min,以充分清除碳纤维布表面的污渍;
(2)将步骤(1)乙醇浸泡过的碳纤维布用去离子水洗清后,然后浸在0.02mol/L稀盐酸中超声振荡5min,以达到去除表面杂质及氧化物;
(3)将稀盐酸浸泡过的碳纤维布用去离子水超声振荡清洗5min,振荡清洗后放入50℃干燥箱中烘干1-2h,称重并保存备用;
(4)配制10.4g/L(0.08mol/L)氯化钴、18.1g/L(0.0.075mol/L)钼酸钠、3.18g/L(0.03mol/L)次亚磷酸钠混合溶液,并加入20g/L硼酸为缓冲剂,0.05g/L丁炔二醇为表面活性剂;滴入稀硫酸调节pH值4;将步骤(3)得到碳纤维布浸泡在混合溶液中进行单脉冲电镀,电源正极连接铂电极,电源负极连接碳纤维布,时间为10min,温度为40℃,电流密度为0.1A/cm2;电镀后将碳纤维布取出,用无水乙醇清洗2-3次,浸入去离子水中超声振荡5min,最后50℃干燥箱中烘干30-45min。即得碳纤维负载CoMoP硼氢化钠水解制氢催化剂。
实施例3
(1)将面密度300g/m2碳纤维布样品浸在无水乙醇中,于25℃超声波振荡清洗10min,以充分清除碳纤维布表面的污渍;
(2)将步骤(1)乙醇浸泡过的碳纤维布用去离子水洗清后,然后浸在0.01mol/L稀盐酸中超声振荡5min,以达到去除表面杂质及氧化物;
(3)将稀盐酸浸泡过的碳纤维布用去离子水超声振荡清洗5min,振荡清洗后放入50℃干燥箱中烘干1-2h,称重并保存备用;
(4)配制15.6g/L(0.12mol/L)氯化钴、30.2g/L(0.125mol/L)钼酸钠、7.42g/L(0.07mol/L)次亚磷酸钠混合溶液,并加入40g/L硼酸为缓冲剂,0.1g/L丁炔二醇为表面活性剂;滴入稀硫酸调节pH值5;将步骤(3)得到碳纤维布浸泡在混合溶液中进行单脉冲电镀,电源正极连接铂电极,电源负极连接碳纤维布,时间为40min,温度为10℃,电流密度为0.3A/cm2;电镀后将碳纤维布取出,用无水乙醇清洗2-3次,浸入去离子水中超声振荡5min,最后50℃干燥箱中烘干30-45min。即得碳纤维负载CoMoP硼氢化钠水解制氢催化剂。
试验例1
采用实施例1相同实验原料和步骤,分别改变氯化钴、钼酸钠和次亚磷酸的浓度;各物质的浓度取值分别如图3、图4和图5所示。
从图3可以看出当氯化钴浓度为0.1mol/l时,制备出来的催化剂性CoMoP/CC产氢催化剂性能最好。
从图4可以看出当钼酸钠浓度为0.1mol/l时,制备出来的CoMoP/CC产氢催化剂性能最好。
从图5可以看出当次亚磷酸钠浓度为0.05mol/l时,制备出来的CoMoP/CC产氢催化剂性能最好。
试验例2
将实施例1制备的CoMoP/CC催化剂进行电镜扫描,其SEM照片如图2所示,而实施例1制备之前碳纤维布载体的SEM照片如图1所示,由图1和2可以发现CoMoP均匀分布在碳纤维布表面且结合致密,说明本发明制备的CoMoP/CC催化剂分布致密;同时实施例2和3制备的CoMoP/CC催化剂的SEM照片与实施例1类似。
试验例3
将实施例1制备的CoMoP/CC催化剂置于硼氢化钠水,考察随着温度变化其产氢性能的变化规律;温度为20-60℃,结果如图6所示。由图6可知本发明制备的催化剂的产氢性能随着温度升高而提升,当温度为60℃产氢速率可以高达11.40L/min·g,说明产氢溶液温度对产氢速率有很大的影响。
同时实施例2和3制备的CoMoP/CC催化剂的在水解制氢性能与实施例1类似。
Claims (1)
1.一种碳纤维布负载CoMoP硼氢化钠水解制氢催化剂的制备方法,其特征在于,包括如下步骤:
(1)将面密度250g/m2碳纤维布样品浸在无水乙醇中,于25℃超声波振荡清洗10min,以充分清除碳纤维布表面的污渍;
(2)将步骤(1)乙醇浸泡过的碳纤维布用去离子水洗清后,然后浸在0.01mol/L稀盐酸中超声振荡5min,以达到去除表面杂质及氧化物;
(3)将稀盐酸浸泡过的碳纤维布用去离子水超声振荡清洗5min,振荡清洗后放入50℃干燥箱中烘干1-2h,称重并保存备用;
(4)配制13g/L氯化钴、24.2g/L钼酸钠、5.3g/L次亚磷酸钠混合溶液,并加入30g/L硼酸为缓冲剂,0.075g/L丁炔二醇为表面活性剂;滴入稀硫酸调节pH值4.5;将步骤(3)得到碳纤维布浸泡在混合溶液中进行单脉冲电镀,电源正极连接铂电极,电源负极连接碳纤维布,时间为25min,温度为25℃,电流密度为0.2A/cm2;电镀后将碳纤维布取出,用无水乙醇清洗2-3次,浸入去离子水中超声振荡5min,最后50℃干燥箱中烘干30-45min, 即得碳纤维布负载CoMoP硼氢化钠水解制氢催化剂。
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