CN107442125B - 一种碳基铜钴氧化物纳米片催化剂的制备方法和应用 - Google Patents
一种碳基铜钴氧化物纳米片催化剂的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种碳基铜钴氧化物纳米片催化剂的制备方法以及基于该催化剂电解水析氧的应用，属于纳米催化、纳米材料、金属有机框架物材料技术领域。其主要步骤将天冬氨酸碱溶液与硝酸铜‑硝酸钴溶液室温共混，室温生成沉淀、抽滤、干燥，制得Cu‑MOF纳米纤维负载Co(II)离子即CuCo‑MOF纳米纤维；将CuCo‑MOF纳米纤维空气氛加热制得。该催化剂制备所用原料成本低，制备工艺简单，反应能耗低，具有工业应用前景。该催化剂用于高效催化电解水析氧，具有良好的析氧电催化活性与电化学稳定性。
Description
技术领域
本发明涉及一种碳基铜钴氧化物纳米片催化剂的制备方法和应用，属于纳米催化、纳米材料、金属有机框架物材料技术领域。
背景技术
由于化石燃料对环境产生的严重污染，制备可持续发展的清洁绿色能源已成为一个重要的前沿研究领域。众所周知，水是地球上含氢氧元素最丰富的资源之一，水分解生成氢气和氧气，氢气放热燃烧又转变为水，该过程再生、清洁和绿色。电催化直接分解水制备氢气和氧气被认为实现该过程最有效的方式。电催化分解水反应包括析氢(hydrogenevolution reaction，HER)和析氧(oxygen evolution reaction，OER)两个半反应，其中，析氢更快，而析氧涉及键裂4个O-H共价键、两个水分子失四个电子以及耗能生成O-O共价键，需要克服更高的能垒才能实现。为此，学者付出了许多努力，开发高效析氧催化剂。在很多已探索的体系中，二氧化铱(IrO2)和二氧化钌(RuO2)被认为最有效。然而，他们稀缺和昂贵的价格，限制了其广泛实际的应用，为此，开发高效、价廉且地球含量丰富的非贵金属析氧催化剂，降低析氧电消耗成为一个机遇和挑战。
价廉的铁、钴、镍催化剂，是已报道实现高活性析氧有前景的催化剂。此外，碳基或杂原子掺杂的复合材料也是析氧催化剂的创新性选择。除了材料组成之外，催化剂的活性和其形态密切相关。为此，研究开发具有资源丰富的新组成和新形态催化剂，对实现高活性析氧具有重要的意义。
作为一类新型多孔晶体材料，近年来，金属有机框架物(MOFs)在气体储存、分离、催化、识别和药物传输等领域获得了广泛的应用。MOFs周期性的多孔结构、高的比表面积以及结构的多样性，提供了以其为前体构建碳或(和)金属基纳米材料的独特优势。目前，源于MOFs前体或模板的功能材料的研究日益增多，例如，多孔碳、金属氧化物、金属/碳和金属氧化物/碳纳米材料已被报道，所构建的3D金属氧化物，用于高效超级电容器、锂离子电池和氧还原，已显现出优异的性质。2014年，Chaikittisilp 和他的团队首次报道了以MOFs为前体制备电催化剂用于分解水的报道，他们采用类沸石Co-MOF (zeolitic imidazolateframework-9, ZIF-9)为前体制备纳米多孔CoxOy-C复合材料电催化OER。因直接高温热解MOFs前体的方法常常导致框架倒塌和团聚，为此，目前常采用的一个创新性策略是利用例如石墨烯、多壁碳纳米管(multiwalled carbon nanotubes，CNTs)的纳米碳材负载MOFs，再通过高温热解制备碳基复合材料电催化剂，以阻止产物团聚并提高其比表面积。例如，2016年，Aijaz和他的团队将Co-MOF在H2氛中高温还原并氧化煅烧，制得了一种Co@Co3O4纳米粒子镶嵌在碳纳米管接枝的氮掺杂的碳多面体高活性析氧催化剂。虽然MOFs种类繁多，但易于制备且转变为可控形态的电催化剂MOFs前体，数量有限，目前，以三维(3D) MOFs微晶或纳米晶体为前体制备析氧催化剂的研究已有报道，据我们所知，基于一维MOFs纳米纤维制备析氧催化剂的研究未见报道。
钴元素地球含量丰富，其氧化物价格低廉，然而，本体钴氧化物导电性差，其电催化析氧活性也差。本开发首先制备了Cu-MOF纳米纤维，在此基础上采用一步室温工艺，制备了负载Co2+纳米纤维CuCo-MOF，以该纳米纤维为前体，在空气中热解，制备了碳基过渡金属氧化物纳米片高效催化剂。
发明内容
本发明的技术任务之一是为了弥补现有技术的不足，提供一种碳基铜钴氧化物纳米片催化剂的制备方法，该方法所用原料成本低，制备工艺简单，反应能耗低，具有工业应用前景。
本发明的技术任务之二是提供所述一种碳基铜钴氧化物纳米片催化剂的用途，即将该碳基铜钴氧化物纳米片用于高效催化电解水析氧，该催化剂具有良好的析氧电催化活性与电化学稳定性。
为实现上述目的，本发明采用的技术方案如下：
1. 一种碳基铜钴氧化物纳米片催化剂的制备方法，步骤如下：
将硝酸铜和硝酸钴共溶于15-18 mL水，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40 mmol 的L-天冬氨酸与0.50-0.58 mmol氢氧化钠溶于2.0 -4.0 mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II) 离子即CuCo-MOF纳米纤维；
将CuCo-MOF纳米纤维置于管式炉加热，制得碳基铜钴氧化物纳米片催化剂；
所述硝酸铜和硝酸钴，总量为0.63-3.28 mmol，硝酸铜与硝酸钴的量比为7：3—5：5；
所述Cu-MOF纳米纤维，化学式为[CuL(H2O)]n，L为天冬氨酸H2L的L(II) 离子；Cu-MOF纳米纤维的一个单元结构，由一个Cu(II)离子中心、一个L(II) 离子和一个H2O分子构成；
所述CuCo-MOF纳米纤维，是由Cu-MOF双纳米线以及3-10个纳米线负载Co(II) 离子沿纵向排列组成，纤维内纳米线间结合紧密，纳米线间晶界清晰可见，纤维表面沿纵向凹凸有序，凹凸尺寸不超过100 nm，纤维纵向最长可达1mm，直径宽约为80-600nm，纤维的横向裂纹也清晰可见；Cu和Co 元素均匀分布；
所述碳基铜钴氧化物纳米片催化剂，其长宽尺寸为8-10μm，厚度小于50 nm；
所述碳基铜钴氧化物纳米片催化剂，是CuO和Co2O3半导体纳米粒子负载在碳微晶上构成的纳米片状复合材料；
所述CuCo-MOF纳米纤维置于管式炉加热，是在空气氛下进行，升温速率为 3-5℃/min，加热至250-300℃，保温1.5-2.5 h，然后，以 2℃/ min 降温速率冷却到室温。
2. 如上所述的碳基铜钴氧化物纳米片作为电解水析氧催化剂的应用，步骤如下：
将6mg 碳基铜钴氧化物纳米片分散于250μL乙醇、720μL 水以及30μL、5 wt%全氟化树脂溶液中，室温120W至少超声10-15min，制得均匀混合液；滴加 6μL该混合液到玻碳电极上，室温干燥，制得碳基铜钴氧化物纳米片工作电极；
使用三电极电化学工作站，碳基铜钴氧化物纳米片工作电极，Pt 片 (5 mm×5 mm×0.1 mm)为对电极，Ag/AgCl电极为参比电极，在电解液为 0.5 M KOH水溶液中测试电催化分解水性能。
上述碳基铜钴氧化物纳米片电解水析氧，当电流密度J=10mA/cm2时，电位为1.50V vs RHE；塔菲尔斜率为67mV dec-1，均说明该材料高效的析氧催化活性；循环 500 次前后，该类材料极化曲线没有发现明显的变化，表明催化剂具有良好的稳定性。
本发明的有益的技术效果：
1. 本发明获得的碳基铜钴氧化物纳米片状催化剂，形貌规整、单一分散，具有高的比表面积等特点。
2. 本发明获得的碳基铜钴氧化物纳米片状催化剂是由一维金属有机框架物CuCo-MOF纳米纤维，空气氛条件250-300℃加热热解生成，制备过程工艺简单，简单易控，产物制备效率高，易于工业化。
3. 本发明提供了一种碳基铜钴氧化物纳米片作为电解水析氧催化剂的应用。由于该催化剂是由CuO和Co2O3半导体纳米粒子负载在碳微晶上构成的纳米片，暴露了更多且不同的活性位点，发挥了CuO、Co2O3半导体纳米粒子以及碳微晶的协同作用，使得基于该复合材料的催化析氧，催化效率高且稳定性好。
具体实施方式
下面结合实施例对本发明作进一步描述，但本发明的保护范围不仅局限于实施例，该领域专业人员对本发明技术方案所作的改变，均应属于本发明的保护范围内。
实施例1
1. 一种碳基铜钴氧化物纳米片催化剂的制备方法
将总量为0.63 mmol、量比为7：3的硝酸铜与硝酸钴共溶于15 mL水，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40 mmol 的L-天冬氨酸与0.50 mmol氢氧化钠溶于2.0 mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II) 离子即CuCo-MOF纳米纤维；
将CuCo-MOF纳米纤维置于管式炉中，空气氛下加热，升温速率为 3℃/min，加热至250℃，保温2.5 h，然后，以 2℃/ min 降温速率冷却到室温，制得碳基铜钴氧化物纳米片催化剂。
实施例2
将总量为3.28 mmol、量比为5：5的硝酸铜与硝酸钴，共溶于18 mL水中，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40 mmol 的L-天冬氨酸与0.58 mmol氢氧化钠溶于4.0mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II) 离子即CuCo-MOF纳米纤维；
将CuCo-MOF纳米纤维置于管式炉中，空气氛下加热，升温速率为 5℃/min，加热至300℃，保温1.5 h，然后，以 2℃/ min 降温速率冷却到室温；制得碳基铜钴氧化物纳米片催化剂；
实施例3
将总量为0.63-3.28 mmol、量比为6：4的硝酸铜与硝酸钴共溶于16.5 mL水，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40 mmol 的L-天冬氨酸与0.55 mmol氢氧化钠溶于3.0 mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II) 离子即CuCo-MOF纳米纤维；
将CuCo-MOF纳米纤维置于管式炉中，空气氛下加热，升温速率为 4℃/min，加热至275℃，保温2.0 h，然后，以 2℃/ min 降温速率冷却到室温。制得碳基铜钴氧化物纳米片催化剂。
实施例4
实施例1-3所述的Cu-MOF纳米纤维，化学式为[CuL(H2O)]n，L为天冬氨酸H2L的L(II) 离子；Cu-MOF纳米纤维的一个单元结构，由一个Cu(II)离子中心、一个L(II) 离子和一个H2O分子构成；
所述CuCo-MOF纳米纤维，是由Cu-MOF双纳米线以及3-10个纳米线负载Co(II) 离子沿纵向排列组成，纤维内纳米线间结合紧密，纳米线间晶界清晰可见，纤维表面沿纵向凹凸有序，凹凸尺寸不超过100 nm，纤维纵向最长可达1mm，直径宽约为80-600nm，纤维的横向裂纹也清晰可见；Cu和Co 元素均匀分布；
所述碳基铜钴氧化物纳米片催化剂，其长宽尺寸为8-10μm，厚度小于50 nm；
所述碳基铜钴氧化物纳米片催化剂，是CuO和Co2O3半导体纳米粒子负载在碳微晶上构成的纳米片状复合材料。
实施例5碳基铜钴氧化物纳米片作为电解水析氧催化剂的应用
分别称取实施例1-3制得的6mg碳基铜钴氧化物纳米片，分散于250μL乙醇、720μL水以及30μL、5 wt%全氟化树脂溶液中，室温120W至少超声10-15min，制得均匀混合液；滴加6μL该混合液到玻碳电极上，室温干燥，制得碳基铜钴氧化物纳米片工作电极；
使用三电极电化学工作站，碳基铜钴氧化物纳米片工作电极，Pt 片 (5 mm×5 mm×0.1 mm)为对电极，Ag/AgCl电极为参比电极，在电解液为 0.5 M KOH水溶液中测试电催化分解水性能；
上述碳基铜钴氧化物纳米片电解水析氧，当电流密度J=10mA/cm2时，电位为1.50V vs RHE；塔菲尔斜率为67mV dec-1，均说明该材料高效的析氧催化活性；循环 500 次前后，该类材料极化曲线没有发现明显的变化，表明催化剂具有良好的稳定性。
Claims (6)
1.一种碳基铜钴氧化物纳米片催化剂的制备方法，其特征在于，步骤如下：
将硝酸铜和硝酸钴共溶于15-18mL水，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40mmol的L-天冬氨酸与0.50-0.58mmol氢氧化钠溶于2.0-4.0mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II)离子即CuCo-MOF纳米纤维；
将CuCo-MOF纳米纤维置于管式炉加热，制得碳基铜钴氧化物纳米片催化剂；所述硝酸铜和硝酸钴，总量为0.63-3.28mmol，硝酸铜与硝酸钴的量比为7：3—5：5；
所述Cu-MOF纳米纤维，化学式为[CuL(H2O)]n，L为天冬氨酸H2L的L(II)离子；Cu-MOF纳米纤维的一个单元结构，由一个Cu(II)离子中心、一个L(II)离子和一个H2O分子构成。
2.如权利要求1所述的一种碳基铜钴氧化物纳米片催化剂的制备方法，其特征在于，所述CuCo-MOF纳米纤维，是由Cu-MOF双纳米线以及3-10个纳米线负载Co(II)离子沿纵向排列组成，纤维内纳米线间结合紧密，纳米线间晶界清晰可见，纤维表面沿纵向凹凸有序，凹凸尺寸不超过100nm，纤维纵向最长可达1mm，直径宽80-600nm，纤维的横向裂纹也清晰可见；Cu和Co元素均匀分布。
3.如权利要求1所述的一种碳基铜钴氧化物纳米片催化剂的制备方法，其特征在于，所述碳基铜钴氧化物纳米片催化剂，其长宽尺寸为8-10μm，厚度小于50nm。
4.如权利要求1所述的一种碳基铜钴氧化物纳米片催化剂的制备方法，其特征在于，所述碳基铜钴氧化物纳米片催化剂，是CuO和Co2O3半导体纳米粒子负载在碳微晶上构成的纳米片状复合材料。
5.如权利要求1所述的一种碳基铜钴氧化物纳米片催化剂的制备方法，其特征在于，所述CuCo-MOF纳米纤维置于管式炉加热，是在空气气 氛下进行，升温速率为3-5℃/min，加热至250-300℃，保温1.5-2.5h，然后，以2℃/min降温速率冷却到室温。
6.如权利要求1所述的制备方法制备的碳基铜钴氧化物纳米片催化剂作为电解水析氧催化剂的应用。
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