CN110292942A - 一种硼氢化钠水解制氢催化剂及其制备方法 - Google Patents

一种硼氢化钠水解制氢催化剂及其制备方法 Download PDF

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CN110292942A
CN110292942A CN201910504090.0A CN201910504090A CN110292942A CN 110292942 A CN110292942 A CN 110292942A CN 201910504090 A CN201910504090 A CN 201910504090A CN 110292942 A CN110292942 A CN 110292942A
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黄文昭
刘广智
罗杏宜
曾宪泰
卜庆元
刘志祥
马东生
陈晓敏
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Foshan (yunfu) Hydrogen Energy Industry And New Materials Development Research Institute
Guangdong Guohong Hydrogen Energy Technology Co ltd
Guohong Hydrogen Energy Technology Jiaxing Co ltd
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Abstract

本发明公开了一种硼氢化钠水解制氢催化剂及其制备方法,制备时,本发明先对载体进行表面改性,利用化学镀在载体表面镀Ni‑P镀层,然后将该含Ni‑P镀层的载体浸入含钌离子的溶液中进行二次化学镀,使载体上Ni‑P镀层的Ni与钌离子发生置换反应,形成Ru‑P镀层。本发明制备方法不仅提高了活性组分Ru‑P于载体上的负载效果,且获得的Ru‑P镀层具有高活性和高稳定性,催化寿命长,适用于大规模生产硼氢化钠制氢系统。

Description

一种硼氢化钠水解制氢催化剂及其制备方法
技术领域
本发明涉及氢能制备技术领域,尤其涉及一种硼氢化钠水解制氢催化剂及其制备方法。
背景技术
随着人类社会的快速发展,一次性的化石能源被大量消耗,使能源短缺和环境污染成为当今世界所面临的主要难题,而氢能是满足人类社会可持续发展和环境友好的重要的新能源之一。氢能可通过氢的燃烧提供热能或通过燃料电池提供电能,而后者是主要的发展方向。燃料电池具有高转换效率,高比功率和比能量,是交通工具的新一代动力源。伴随着燃料电池技术的不断突破和商业化前景的不断明朗,燃料电池的氢源技术也越来越受到重视。如何安全、高效地储氢是急需解决的问题。
硼氢化钠具有常温稳定、储存方法简单等优势,而硼氢化钠水解制氢技术可方便、实用、高效地获得高纯氢气,是质子交换膜燃料电池的最佳氢源之一。硼氢化钠水解时,添加高效催化剂可获得高的产氢速率,实现反应的快速启动。常用的催化剂包括钌、铂等贵金属催化剂以及镍、钴等过渡金属催化剂。为了降低成本,贵金属催化剂在实际应用中,通常负载在载体上,起到了减少用量及提高稳定性的效果。现有技术中,催化剂的负载方法主要有化学镀法和电镀法。其中,化学镀法一般是直接在载体上实施化学镀,镀层效果差,催化剂的催化活性不高,催化寿命较短,且稳定性较低。而电镀法虽然能获得活性较高的催化剂,但需专门的电镀设备,且电镀耗时较长,对工艺的要求较高,不适合大规模生产使用。
发明内容
为解决上述现有技术中存在的缺点和不足,本发明的目的在于提供一种硼氢化钠水解制氢催化剂及其制备方法。本发明先对载体进行表面改性,利用化学镀在载体表面镀Ni-P镀层,然后将该含Ni-P镀层的载体浸入含钌离子的溶液中进行二次化学镀,使载体上Ni-P镀层的Ni与钌离子发生置换反应,形成Ru-P镀层。本发明制备方法不仅提高了活性组分Ru-P于载体上的负载效果,且获得的Ru-P镀层具有高活性和高稳定性,催化寿命长,适用于大规模生产硼氢化钠制氢系统。
为实现其目的,本发明采取的技术方案为:
一种硼氢化钠水解制氢催化剂的制备方法,其包括如下步骤:
(1)化学镀法载Ni-P:
a:将镍盐和还原剂用去离子水溶解,加入助剂调节pH至4~6,得到溶液A;
b:将载体浸入所述溶液A中,在50~100℃下加热1~6h,过滤,用去离子水洗涤固体产物,干燥,备用;
(2)化学镀法载钌:
c:配制浓度为0.1~10g/L、pH为2~6的钌盐溶液;
d:将步骤b制得的固体产物浸入所述钌盐溶液中,在0~50℃下浸渍8~16h,过滤,用去离子水洗涤固体产物,干燥,制得目标产物。
优选地,所述镍盐与还原剂的质量比为1:1~1:20。在上述配比下,更利于在载体表面建立良好致密的Ni-P镀层,且使后续钌与镍的置换效果更好,形成稳定的Ru-P镀层。最优选地,所述镍盐与还原剂的质量比为1:3。
优选地,所述镍盐为氯化镍、硫酸镍、硝酸镍中的至少一种。
优选地,所述还原剂为次亚磷酸钠、次亚磷酸、次亚磷酸钾、亚磷酸钠中的至少一种。
优选地,所述助剂为有机酸、有机酸缓冲液、无机酸中的至少一种。优选地,所述有机酸为醋酸、柠檬酸中的至少一种。优选地,所述有机酸缓冲液为醋酸-醋酸钠缓冲液、柠檬酸-柠檬酸钠缓冲液中的至少一种。优选地,所述无机酸为盐酸、硫酸中的至少一种。
优选地,所述载体为金属骨架材料。优选地,所述金属骨架材料为泡沫镍、铜片、不锈钢网中的至少一种。金属骨架材料有利于传热和传质,减少局部温差和浓度差,利于化学反应及良好镀层的形成。
优选地,所述干燥的温度为30~300℃,时间为12~24h。
优选地,所述钌盐为三氯化钌、醋酸钌、二茂钌中的至少一种。
与现有技术相比,本发明的有益效果为:本发明先对载体进行表面改性,利用化学镀在载体表面镀Ni-P镀层,然后将该含Ni-P镀层的载体浸入含钌离子的溶液中进行二次化学镀,使载体上Ni-P镀层的Ni与钌离子发生置换反应,形成Ru-P镀层。本发明制备方法不仅提高了活性组分Ru-P于载体上的负载效果,且获得的Ru-P镀层具有高活性和高稳定性,催化寿命长,适用于大规模生产硼氢化钠制氢系统。
附图说明
图1为实施例1~4和对比例1制得的催化剂的产氢效果图;
图2为试验组1~6的产氢效果图。
具体实施方式
为更好的说明本发明的目的、技术方案和优点,本发明通过下列实施例进一步说明。应理解,本发明实施例仅用于说明本发明的技术效果,而非用于限制本发明的保护范围。实施例中,所用方法如无特别说明,均为常规方法。
实施例1
一种硼氢化钠水解制氢催化剂的制备方法,其包括如下步骤:
(1)化学镀法载Ni-P
称取1g硫酸镍和1g次亚磷酸于烧杯中,加入适量去离子水溶解,然后用柠檬酸-柠檬酸钠缓冲液调节pH至4,定容至100mL,得到溶液A。称取10g铜片,倒入溶液A中,在100℃下加热1h,过滤,用去离子水冲洗固体产物,然后在60℃恒温干燥箱中干燥12h,备用。
(2)化学法镀钌
配制醋酸钌溶液(0.1g L-1醋酸钌和0.1mol/L醋酸-醋酸钠缓冲液)100mL,将步骤(1)制得的固体产物浸入醋酸钌溶液中,50℃下浸渍8h,过滤,用去离子水冲洗3~5次,300℃恒温干燥12h,制得所述硼氢化钠水解制氢催化剂。
实施例2
一种硼氢化钠水解制氢催化剂的制备方法,其包括如下步骤:
(1)化学镀法载Ni-P
称取1.8g氯化镍和2.5g次亚磷酸钠于烧杯中,加入适量去离子水溶解,然后用醋酸-醋酸钠缓冲液调节pH至4.75,定容至100mL,得到溶液A。称取10g泡沫镍,倒入溶液A中,在70℃下加热3h,过滤,用去离子水冲洗固体产物,然后在40℃恒温干燥箱中干燥18h,备用。
(2)化学法镀钌
配制三氯化钌溶液(2g L-1三氯化钌和40mL L-1盐酸)100mL,将步骤(1)制得的固体产物浸入三氯化钌溶液中,室温(25℃)下浸渍13h,过滤,用去离子水冲洗3~5次,40℃恒温干燥18h,制得所述硼氢化钠水解制氢催化剂。
实施例3
一种硼氢化钠水解制氢催化剂的制备方法,其包括如下步骤:
(1)化学镀法载Ni-P
称取1.2g氯化镍和2.5g次亚磷酸钠于烧杯中,加入适量去离子水溶解,然后用醋酸调节pH至5,定容至100mL,得到溶液A。称取10g泡沫镍,倒入溶液A中,在80℃下加热2h,过滤,用去离子水冲洗固体产物,然后在40℃恒温干燥箱中干燥18h,备用。
(2)化学法镀钌
配制三氯化钌溶液(4g L-1三氯化钌和40mL L-1盐酸)100mL,将步骤(1)制得的固体产物浸入三氯化钌溶液中,室温(25℃)下浸渍13h,过滤,用去离子水冲洗3~5次,40℃恒温干燥18h,制得所述硼氢化钠水解制氢催化剂。
实施例4
一种硼氢化钠水解制氢催化剂的制备方法,其包括如下步骤:
(1)化学镀法载Ni-P
称取1g硝酸镍和20g亚磷酸钠于烧杯中,加入适量去离子水溶解,然后用盐酸调节pH至4,定容至100mL,得到溶液A。称取10g不锈钢网,倒入溶液A中,在50℃下加热6h,过滤,用去离子水冲洗固体产物,然后在30℃恒温干燥箱中干燥24h,备用。
(2)化学法镀钌
配制三氯化钌溶液(10g L-1三氯化钌和3%的醋酸)100mL,将步骤(1)制得的固体产物浸入三氯化钌溶液中,0℃下浸渍16h,过滤,用去离子水冲洗3~5次,30℃恒温干燥24h,制得所述硼氢化钠水解制氢催化剂。
对比例1
一种硼氢化钠水解制氢催化剂的制备方法,其包括如下步骤:
配制三氯化钌溶液(2g L-1三氯化钌和40mL L-1盐酸)100mL,将10g泡沫镍浸入三氯化钌溶液中,室温(25℃)下浸渍13h,过滤,用去离子水冲洗3~5次,40℃恒温干燥18h,制得所述硼氢化钠水解制氢催化剂。
对实施例1~4和对比例1制得的催化剂进行测试,结果如图1所示:
从图1可看出,实施例1~4制得的催化剂在产氢时间和产氢速度上均显著优于对比例1,说明本发明提供的硼氢化钠水解制氢催化剂具备高活性、高稳定性和长催化寿命等优点。
为探究镍盐与还原剂的质量比对化学镀的影响,设计试验组6组,各试验组的镍盐与还原剂的种类和用量如表1所示。
表1
将试验组1~6按实施例3的制备方法制备硼氢化钠水解制氢催化剂,并测试催化剂的性能,测试结果如图2所示:
图2中,1、2、3、4、5、6分别代表试验组1、试验组2、试验组3、试验组4、试验组5、试验组6。从图2可看出,试验组3的产氢性能显著优于其他试验组,说明镍盐与还原剂的质量比为1:3时,形成的Ni-P镀层与Ru-P镀层的效果最好。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。

Claims (10)

1.一种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)化学镀法载Ni-P:
a:将镍盐和还原剂用去离子水溶解,加入助剂调节pH至4~6,得到溶液A;
b:将载体浸入所述溶液A中,在50~100℃下加热1~6h,过滤,用去离子水洗涤固体产物,干燥,备用;
(2)化学镀法载钌:
c:配制浓度为0.1~10g/L、pH为2~6的钌盐溶液;
d:将步骤b制得的固体产物浸入所述钌盐溶液中,在0~50℃下浸渍8~16h,过滤,用去离子水洗涤固体产物,干燥,制得目标产物。
2.如权利要求1所述的硼氢化钠水解制氢催化剂的制备方法,其特征在于,所述镍盐与还原剂的质量比为1:1~1:20。
3.如权利要求2所述的硼氢化钠水解制氢催化剂的制备方法,其特征在于,所述镍盐与还原剂的质量比为1:3。
4.如权利要求1所述的硼氢化钠水解制氢催化剂的制备方法,其特征在于,所述镍盐为氯化镍、硫酸镍、硝酸镍中的至少一种。
5.如权利要求1所述的硼氢化钠水解制氢催化剂的制备方法,其特征在于,所述还原剂为次亚磷酸钠、次亚磷酸、次亚磷酸钾、亚磷酸钠中的至少一种。
6.如权利要求1所述的硼氢化钠水解制氢催化剂的制备方法,其特征在于,所述助剂为有机酸、有机酸缓冲液、无机酸中的至少一种;优选地,所述有机酸为醋酸、柠檬酸中的至少一种;优选地,所述有机酸缓冲液为醋酸-醋酸钠缓冲液、柠檬酸-柠檬酸钠缓冲液中的至少一种;优选地,所述无机酸为盐酸、硫酸中的至少一种。
7.如权利要求1所述的硼氢化钠水解制氢催化剂的制备方法,其特征在于,所述载体为金属骨架材料;优选地,所述金属骨架材料为泡沫镍、铜片、不锈钢网中的至少一种。
8.如权利要求1所述的硼氢化钠水解制氢催化剂的制备方法,其特征在于,所述干燥的温度为30~300℃,时间为12~24h。
9.如权利要求1所述的硼氢化钠水解制氢催化剂的制备方法,其特征在于,所述钌盐为三氯化钌、醋酸钌、二茂钌中的至少一种。
10.一种硼氢化钠水解制氢催化剂,其特征在于,由如权利要求1~9任一项所述的硼氢化钠水解制氢催化剂的制备方法制得。
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