CN111485249B - 一种提高铁基非晶合金催化析氢性能的方法 - Google Patents
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Abstract
本发明公开了一种提高铁基非晶合金催化析氢性能的方法,涉及电解水催化剂领域。该提高铁基非晶合金催化析氢性能的方法包括如下步骤:(1)采用电化学工作站三电极体系,以铁基非晶合金带材为工作电极,H2SO4为电解液,在析氢反应体系中进行循环伏安扫描、活化该铁基非晶合金带材;(2)利用强氧化性溶液浸蚀活化后的铁基非晶合金带材。本发明先通过循环伏安法处理非晶合金带材,显著增大了非晶合金带材的活性比表面积,使铁基非晶合金的析氢过电位明显降低,有效解决了带材活性比表面积小的问题;然后通过HNO3溶液浸蚀活化后的非晶合金带材,使其表面钝化,克服了铁基非晶催化剂在酸性条件下易腐蚀的问题,提高了催化剂长期有效工作的稳定性。
Description
技术领域
本发明涉及一种提高铁基非晶合金催化析氢性能的方法,属于电解水制氢催化剂技术领域。
背景技术
随着经济发展所带来的能源危机以及环境污染问题,氢气,作为一种清洁、高效、可再生能源,极具发展前景。电解水是生产高纯度氢,发展可持续能源的重要途径,水电解由阴极析氢(HER)和阳极析氧(OER)两个半反应构成,但由于动力学阻碍,驱动水分解制氢往往耗能大、效率低,因此需要开发电解水催化剂来降低能耗,提高能量转化率。
目前商用催化剂主要是贵金属Pt、Ir或其氧化物,但是价格昂贵且储量稀缺,所以亟待开发低成本且高效的非贵金属催化剂。过渡金属,以Fe、Co、Ni为主,由于具有不完全填充的d轨道而具有较高的催化活性,有望替代贵金属催化剂。现有研究主要集中于一系列过渡金属的硫化物、磷化物、碳化物以及氮化物。相比于过渡金属晶态催化剂,非晶合金不仅反应活性位点多,而且耐腐蚀性能佳;相比于粉末催化剂,熔体旋淬法所制备的韧性非晶带材还可自支撑,直接用作电极,更适合工业应用。所以非晶合金,尤其带状非晶,成为一种具有发展前途的催化材料。
近年来,非贵金属基非晶合金催化剂的研究主要围绕于镍基合金、铁基合金,通常镍基合金适合在碱性环境下工作,而铁基合金在酸性环境下具有更佳的析氢催化活性。铁不仅储量丰富、成本低,而且非晶态铁合金成分多样,但因在酸性条件下易腐蚀,所以极大的限制了铁基非晶作为析氢催化剂的应用。通过贵金属元素如Pd、Pt掺杂可改善催化剂的稳定性,但也增加了成本。
根据目前铁基非晶合金作为析氢电极材料的报道发现,铁基非晶合金析氢催化活性也有待进一步提升。如公开号为CN 107217219 A的中国专利申请公开了一种用于高效析氢反应的Fe-Co-P-C系非晶电催化剂及其制备方法,该专利通过熔体旋淬法制备的Fe40Co40P13C7非晶合金带材,在电流密度为10mA cm-2时,酸性析氢过电位为124mV。公开号为CN 109023161 A的中国专利申请公开了一种Fe-Ni-P-C系非晶合金电催化剂及其制备方法和应用,成分为Fe70Ni10P13C7的非晶合金带材性能最佳,在电流密度为10mA cm-2时,酸性析氢过电位为120mV。虽然上述催化剂的成本均显著降低了,但过电位仍明显高于商用催化剂Pt/C(37mV),这主要归因于非晶带材本身活性比表面积较小,不具备粗糙或纳米多孔表面暴露多活性位点的优势。
由上可知,铁基非晶合金作为析氢电极材料仍存在不少挑战。基于此,进一步提升可自支撑铁基非晶合金电催化活性,克服铁基非晶催化剂在酸性条件下稳定性差的问题,提供一种提高铁基非晶合金催化析氢性能的方法,对非晶合金带材在催化电解水方面的应用具有重要意义。
发明内容
发明目的:针对现有铁基非晶合金带材活性比表面积较小、铁基非晶催化剂在酸性条件下稳定性差的问题,本发明提供一种提高铁基非晶合金催化析氢性能的方法。
技术方案:本发明所述的一种提高铁基非晶合金催化析氢性能的方法,包括如下步骤:
(1)采用电化学工作站三电极体系,以铁基非晶合金带材为工作电极,H2SO4为电解液,在析氢反应体系中进行循环伏安扫描、活化该铁基非晶合金带材;
(2)利用强氧化性溶液浸蚀活化后的铁基非晶合金带材。
上述铁基非晶合金为Fe-R-P-C系非晶合金,其中,R为Co、Ni、Mo中的一种。较优的,该Fe-Mo-P-C系非晶合金的制备步骤包括:
A、以高纯Fe、Mo、FeP、C为原料,在高纯氩气氛围下,采用电弧熔炼、感应熔炼制备母合金锭,并对母合金锭多次重熔以确保合金成分均匀;
B、通过熔体旋淬法制备Fe-Mo-P-C系非晶合金带材。
当铁基非晶合金为Fe-Mo-P-C系非晶合金时,步骤(1)中,循环伏安扫描电压范围为-0.19~0.16V vs RHE。较优的,该Fe-Mo-P-C系非晶合金的组成为Fe80-xMoxP13C7,其中4≤x≤10,x为元素Mo的原子百分数。
上述步骤(1)中,优选的,循环伏安扫描速度为10~100mV s-1,当扫描获得的循环伏安曲线不再变化时,即前后数次循环伏安曲线重合时,停止扫描。
步骤(2)中,强氧化性溶液优选为HNO3溶液或H2SO4溶液。最好为HNO3溶液,其浓度优选为7.2~9.6M,浸蚀反应时间为10~30min。浸蚀反应可在常温下进行。
有益效果:与现有技术相比,本发明的优点为:本发明先通过循环伏安法处理非晶合金带材,显著增大了非晶合金带材的活性比表面积,使铁基非晶合金的析氢过电位明显降低;然后通过强氧化性溶液如HNO3溶液浸蚀活化后的非晶合金带材,使其表面钝化,克服了铁基非晶催化剂在酸性条件下易腐蚀的问题,提高了催化剂长期有效工作的稳定性。
附图说明
图1为实施例1制备的Fe-Mo-P-C系非晶合金带材的X射线衍射图谱;
图2为实施例1制备的Fe76Mo4P13C7非晶合金带材在0.5M H2SO4电解液中的循环伏安曲线;
图3为实施例1和实施例2制备的Fe-Mo-P-C系非晶合金带材在0.5M H2SO4电解液中的LSV曲线;
图4为实施例1和实施例2制备的Fe76Mo4P13C7非晶合金带材在0.5M H2SO4电解液中循环伏安曲线扫描速度与双层电容电流密度关系图;
图5为实施例1和实施例2制备的Fe76Mo4P13C7非晶合金带材在0.5M H2SO4电解液中10mA cm-2电流密度下的V-t曲线。
具体实施方式
下面结合附图对本发明的技术方案作进一步说明。
本发明的一种提高铁基非晶合金催化析氢性能的方法,包括如下步骤:
(1)采用电化学工作站三电极体系,以铁基非晶合金带材为工作电极,H2SO4为电解液,在析氢反应体系中进行循环伏安扫描、活化该铁基非晶合金带材;
(2)利用强氧化性溶液浸蚀活化后的铁基非晶合金带材。
通过循环伏安法处理铁基非晶合金带材,可明显增大铁基非晶合金带材的活性比表面积,使铁基非晶合金的析氢过电位显著降低;通过强氧化性溶液如HNO3溶液浸蚀活化后的非晶合金带材,使其表面钝化,可提高铁基非晶合金催化剂在酸性环境工作的稳定性。
下述实施例以Fe-Mo-P-C系非晶合金Fe80-xMoxP13C7(4≤x≤10)为例,对本发明的方法进行详细说明。
实施例1
分别制备Fe76Mo4P13C7非晶合金带材和Fe70Mo10P13C7非晶合金带材。
制备过程具体如下:
(1)将高纯Fe、Mo、FeP、C按原子百分比换算称量,在高纯氩气氛围下,首先将Fe、Mo、C通过电弧熔炼成合金锭,对合金锭至少重熔4次以确保合金成分均匀,然后将合金锭与FeP混合,进行感应熔炼;
(2)采用单辊甩带设备,将母合金锭Fe80-xMoxP13C7(x=4,10)在氩气氛围中进行感应熔化,通过瞬时压差(0.02MPa)将金属液喷到转速为40m/s的铜辊上,获得宽1~3mm,厚20~30μm的Fe80-xMoxP13C7(x=4,10)合金带材。
取部分制备的Fe76Mo4P13C7合金带材和Fe70Mo10P13C7合金带材分别经去离子水、无水乙醇超声清洗,自然干燥后,剪成长为2cm的短带材。
图1所示为Fe76Mo4P13C7合金带材及Fe70Mo10P13C7合金带材的X射线衍射图谱,可以看到,XRD图谱上只有漫散射峰,说明制得的Fe76Mo4P13C7合金带材及Fe70Mo10P13C7合金带材均为非晶态结构。
实施例2
对实施例1制得的Fe76Mo4P13C7非晶合金带材及Fe70Mo10P13C7非晶合金带材分别进行循环伏安扫描活化和HNO3溶液浸蚀处理。
以Fe76Mo4P13C7非晶合金带材为例,活化及浸蚀步骤如下:
(1)以实施例1制备的长为2cm的Fe76Mo4P13C7非晶合金带材为工作电极,Ag/AgCl为参比电极,石墨棒为对电极,在0.5M H2SO4电解液中,以10mV s-1的扫描速度在-0.19~0.16V vs RHE电压范围内进行循环伏安扫描(CV),当循环伏安曲线重合时,停止扫描。
图2为Fe76Mo4P13C7非晶合金带材的循环伏安曲线,由图可知,随着循环伏安扫描次数增加,阴极极化曲线下移并趋于重合,循环伏安曲线说明电催化剂的析氢性能有所提升,而该提升是有极限的。
(2)将经循环伏安法活化后的Fe76Mo4P13C7非晶合金带材浸蚀在浓度为9.6M的HNO3溶液中,20min后取出,并依次用去离子水和无水乙醇清洗,去除非晶合金带材表面残留的化学物质。
实施例3
对实施例1制备的Fe80-xMoxP13C7(x=4,10)非晶合金带材、实施例2中循环伏安扫描活化后的非晶合金带材以及HNO3溶液浸蚀处理后的非晶合金带材分别进行电化学性能测试。
(1)在0.5M H2SO4电解液中,分别以实施例1制备的非晶合金带材和实施例2制备的循环伏安扫描活化后的非晶合金带材为工作电极,Ag/AgCl为参比电极,石墨棒为对电极,以5mV s-1的扫速进行线性扫描伏安测试。
图3为活化前后Fe80-xMoxP13C7(x=4,10)非晶合金带材的LSV曲线,可以看到在电流密度为10mA cm-2时,活化前的Fe76Mo4P13C7、Fe70Mo10P13C7的过电位分别为:165mV、283mV;活化后的Fe76Mo4P13C7、Fe70Mo10P13C7的过电位分别为:96mV、161mV,活化后,催化剂的析氢过电位明显降低。
(2)在0.5M H2SO4电解液中,分别以实施例1制备的Fe76Mo4P13C7非晶合金带材和实施例2制备的循环伏安法活化后的Fe76Mo4P13C7非晶合金带材为工作电极,Ag/AgCl为参比电极,石墨棒为对电极,以10mV s-1、20mV s-1、30mV s-1、40mV s-1、50mV s-1的扫速测循环伏安曲线。
图4为活化前后Fe76Mo4P13C7非晶合金带材的循环伏安曲线扫描速度与双层电容电流密度关系图,由图可知,经循环伏安法活化后,Fe76Mo4P13C7的电容值由26mF cm-2提升至316mF cm-2,表明活化后催化剂的活性面积显著增大,即活性位点增多,与活化后Fe76Mo4P13C7析氢过电位显著降低这一结果相吻合。
(3)在0.5M H2SO4电解液中,分别以实施例2制备的循环伏安法活化后的Fe76Mo4P13C7非晶合金带材和循环伏安法活化并硝酸浸蚀后的Fe76Mo4P13C7非晶合金带材为工作电极,Ag/AgCl为参比电极,石墨棒为对电极。通过计时电位法,测试以Fe76Mo4P13C7非晶合金作为析氢催化剂在12h内的稳定性。
图5为硝酸处理前后活化的Fe76Mo4P13C7非晶合金带材的V-t曲线,可以看到,未经硝酸浸蚀处理的非晶合金带材,12h测试后过电位增加28mV,而经硝酸处理后的非晶合金带材,12h测试后过电位仅增加5mV,可见,经过进一步HNO3溶液浸蚀处理的Fe76Mo4P13C7非晶合金稳定性明显提升,这可能是因为非晶合金表面生成的氧化层阻止了非晶合金内部原子在反应过程中继续被腐蚀。
综上可知,通过循环伏安法对Fe-Mo-P-C系非晶合金带材进行活化,可增大其活性面积,显著降低非晶合金的析氢过电位;进一步通过HNO3溶液浸蚀活化后的非晶合金带材,对其进行表面处理,可提升非晶合金作为催化剂在酸性环境下长期有效工作的稳定性。
Claims (4)
1.一种提高铁基非晶合金催化析氢性能的方法,其特征在于,包括如下步骤:
(1)采用电化学工作站三电极体系,以铁基非晶合金带材为工作电极,H2SO4为电解液,在析氢反应体系中进行循环伏安扫描、活化该铁基非晶合金带材;所述铁基非晶合金为Fe80-xMoxP13C7,其中4≤x≤10,x为元素Mo的原子百分数;
(2)利用强氧化性溶液浸蚀活化后的铁基非晶合金带材;所述强氧化性溶液为HNO3溶液。
2.根据权利要求1所述的提高铁基非晶合金催化析氢性能的方法,其特征在于,所述步骤(1)中,循环伏安扫描电压范围为-0.19~0.16V vs RHE。
3.根据权利要求1所述的提高铁基非晶合金催化析氢性能的方法,其特征在于,步骤(1)中,所述循环伏安扫描速度为10~100mV s-1,当扫描获得的循环伏安曲线不再变化时,停止扫描。
4.根据权利要求1所述的提高铁基非晶合金催化析氢性能的方法,其特征在于,所述HNO3溶液浓度为7.2~9.6M,浸蚀反应时间为10~30min。
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