CN116281887A - 一种硒化铌六方片的制备方法及应用 - Google Patents
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Abstract
本发明为一种硒化铌六方片的制备方法及应用。将铌粉、硒粉以摩尔比为0.2:1均匀混合后压制成片，放入直流电弧等离子体放电装置内水平放置的阴阳极之间。在水冷系统和氩气氛围的保护下，将气压升至40‑60kPa，反应电流为40‑100A，阴阳两极极间起弧放电，反应完全后冷却钝化至室温。在石墨锅内收集到灰黑色粉末，微观形貌为厚度介于0.2‑0.4μm，直径范围为0.5‑2μm的硒化铌六方片。将硒化铌六方片作为析氢反应催化剂，在5mV·s‑1的扫速下，NbSe2六方片在‑10mA·cm‑2的电流密度下可实现255mV的过电势，表明NbSe2六方片有良好的析氢催化活性。
Description
技术领域
本发明属于无机纳米材料制备领域，提供一种析氢反应催化剂硒化铌六方片的制备方法及应用。
背景技术
典型稀有贵金属铂(Pt)及其合金是当前最有效的析氢反应(HER)催化剂，由于Pt稀有且价格昂贵，难以规模化应用，开发具有相对低廉的成本、高的活性、良好的稳定性和高导电性的非贵金属高效的HER催化剂材料备受关注。过渡金属硫属化合物AB2(A代表过渡金属元素，B代表S、Se等元素)，具有准二维层状结构和较高的电催化析氢活性，因此可替代贵金属作为高效HER电催化剂候选材料。目前，研究最多的VI族过渡金属硫属化合物H-MoS2和H-WS2，由于暴露的硫族边缘位点充当HER活性位点，而更丰富的基面则显催化惰性，同时材料的半导体属性也限制电子向催化边缘位点的转移，导致活性位点数量的不足，从而抑制电解槽系统中高H2的生产速率。硒化铌(NbSe2)属于一种典型的V族过渡金属硫属化合物，依据NbSe2分子层的堆叠形式不同，呈现出六方(2H相)或菱方(3R相)的晶体构型，其中六方H相被认为是热力学最稳定相。NbSe2的晶体结构同第VI族AB2化合物结构相似，均为典型的六方层状结构，在室温下NbSe2具有卓越的金属性质，电阻率仅为10-4Ω·cm，比MoS2小六个数量级，而在低温(约7.0K)下表现出超导特性。从先前大量的研究可知NbSe2的基面存在丰富的析氢活性位点，因其自身的金属性质和基面活性，NbSe2在电催化方面呈现出高活性的HER催化性能。
目前，合成NbSe2的方法主要有化学气相沉积法、液相剥离法、分子束外延法和真空固相烧结法等。Wang(Ionics,25,2019,4171)等人采用真空固相烧结方法，将铌粉和硒粉前驱体密封在真空石英管中，在750℃下煅烧3h，合成了NbSe2薄膜,此方法需要预先对原材料进行处理，制成前驱体，制备NbSe2所耗时间长、操作繁琐且样品量有限。Yang(Nanomaterials,9,2019,751)等人以H2O2为造孔剂，采用双超声液相剥离法制备了单层NbSe2多孔纳米片，虽表现出优异的电催化活性，但难以去除的表面活性剂和残留的H2O2会对样品性能有明显影响，制备过程中要用到表面活性剂、有机溶剂和强酸来剥离和稳定NbSe2纳米片，所以此方法会导致长期环境污染问题。Wang(Nature Communications,8,2017,394)等人采用化学气相沉积法实现了NbSe2单层材料的生长，此方法需要用部分氧化铌原料作为生长NbSe2的前驱体，生长的NbSe2材料中不可避免的包含少量杂质。传统NbSe2合成方法一般采用预制前驱体、过量的原料或者以化学计量比进行NbSe2材料的合成，原材料成本较高、耗时长、反应温度较高、环境不友好、产出率低等缺点。因此，从经济成本和绿色环保角度考虑，亟需开发一种经济、快速、高效、稳定的合成途径。本发明提供了一种少铌条件下一步制备NbSe2的方法，以铌和硒摩尔比为0.2:1的条件下获得纯净的NbSe2产物，与传统方法相比减少原材料损耗和成本，并用做电催化HER活性材料。
发明内容
本发明提供了一种操作简单、成本低廉的一步制备硒化铌六方片的方法，以铌和硒摩尔比为0.2:1(化学计量比0.5:1)的比例合成NbSe2，所需原料成本降低且避免原料浪费，环境友好，同时合成出的产物产量高，可用作析氢电催化活性材料。
本发明的具体操作过程如下：
1.将铌粉、硒粉以0.2:1的摩尔比称量后放入玛瑙研钵中，研磨30min，使铌粉和硒粉均匀混合。将研磨后的铌、硒混合粉末放入压片模具中，经过加压、保压、卸压过程压成高度约为2.5mm的圆片。
2.将压好的样品圆片放进水平式直流电弧等离子体放电装置内的阳极石墨锅中，阴极为钨棒，调整阴极钨棒和阳极石墨锅的水平轴线重合，阴阳两极间距约1cm。
3.关闭反应装置，进行抽气—洗气—抽气过程，至少重复三次，洗气后将装置内气压抽至10Pa以下。在冷却循环水和氩气氛围的保护下，将装置内气压升至40-60kPa。启动电弧电源，设置电流为40-100A，调整阴阳两极的间距进行引弧，起弧稳定后保持10min直至反应完全，关闭直流弧焊机电源。
4.在水冷系统和氩气氛围中冷却钝化1-3h。在阳极石墨锅内收集到的灰黑色粉末为NbSe2六方片。
5.将制备的NbSe2六方片直接作为活性物质，获得低电荷转移电阻和高电子转移速率的析氢反应催化剂。
本发明比现有技术的优势在于以少铌的条件制备出纯相的NbSe2，大大减少了原料的消耗，并且制备工艺简单、稳定性高、节约成本、安全环保、可重复性高，一步获得纯净的NbSe2六方片，直接用作析氢反应的催化剂。
附图说明
图1直流电弧等离子体放电装置结构示意图。
图2NbSe2六方片的X射线衍射(XRD)图。
图3NbSe2六方片的低倍率扫描电子显微镜(SEM)图。
图4NbSe2六方片的高倍率扫描电子显微镜(SEM)图。
图5NbSe2六方片的透射电子显微镜(TEM)图。
图6NbSe2六方片的高分辨透射电子显微镜(HRTEM)图和选区电子衍射(SAED)图。
图7NbSe2六方片的线性扫描伏安特性(LSV)曲线图。
图8NbSe2六方片的塔菲尔(Tafel)曲线图。
图9NbSe2六方片的奈奎斯特(Nyquist)图。
具体实施方式
实施例1直流电弧等离子体放电装置
图1为直流电弧等离子体放电装置结构示意图。水冷系统的重要性在于：①反应前，通入循环冷却水，保证设备安全运转。外层冷却水从进水口2流入，经过整个外层腔体1，并从出水口3流出；内层冷却水从进水口5流入，经过内层水冷套筒4，从出水口6流出；阳极冷却水从进水口7流入，从出水口8流出。②反应中，循环水冷区和高温电弧之间产生的温度梯度是产生纯净的NbSe2的必备条件。③反应后，水冷系统起到冷却钝化的作用。
实施例2NbSe2六方片的制备全过程及电化学性能测试
按照摩尔比0.2:1分别称量铌粉0.2g和硒粉0.85g，放入玛瑙研钵中研磨30min，使二者均匀混合。把研磨后的混合物放入压片机模具中，压制成高度为2.5mm、直径尺寸为1cm的圆柱形薄片。将圆片放入水平放置的阳极石墨锅中，固定在装置内一侧。阴极钨棒固定在反应装置内另一侧，与阳极石墨锅的水平轴线重合，调节阴阳两极间距约1cm。封闭反应装置，反复洗气至少三次，将装置内气压抽至10Pa以下。在水冷系统和氩气氛围的保护下将装置内气压升至40kPa。启动电弧电源，设置反应电流为40A，进行起弧放电，反应持续10min后停止放电。在水冷系统和在氩气氛围中冷却钝化3h至室温，在阳极石墨锅内收集的灰黑色粉末为NbSe2六方片。
将制备的NbSe2六方片直接作为活性物质，以乙炔黑为导电剂，PTFE(聚四氟乙烯)为粘结剂，NMP(N-甲基吡咯烷酮)为溶剂，按活性物质:导电剂:粘结剂＝8:1:1的质量比混合，涂覆在面积为1cm2的碳布上作为工作电极。以石墨棒为对电极，汞/氧化汞为参比电极，0.5M的硫酸溶液为电解液，测试前用氢气进行预处理，在5mV·s-1的扫速下进行线性扫描伏安法测量。电化学测试均利用普林斯顿电化学工作站。
图2给出实施例2制得的NbSe2六方片的X射线衍射(XRD)图，所有衍射峰峰位均与JCPDS no.87-2415标准卡片相匹配。三强峰分别位于2θ角30.76°、33.16°、41.70°处，分别对应(101)、(102)、(104)晶面。可知获得的产物为纯净无杂质的NbSe2。
图3给出NbSe2六方片低倍率的扫描电子显微镜(SEM)图。从图中可以清晰的看到，产物NbSe2大多为六方片状。六方片状的NbSe2厚度介于0.2-0.4μm，直径范围0.5-2μm。图4给出NbSe2六方片的高倍率扫描电子显微镜(SEM)图。可以清晰的看到是一个形状非常完好的NbSe2六方片。
图5为NbSe2六方片的透射电子显微镜(TEM)图。图中NbSe2六方片微观形貌与SEM结果一致。图6给出NbSe2六方片所对应的高分辨透射电子显微镜(HRTEM)图，经测算晶格条纹的间距d值为
表明NbSe2六方片沿(110)面生长。插图给出NbSe2六方片所对应的选区电子衍射(SAED)图，图中规则排列的衍射斑点表明NbSe2六方片的单晶性质。
图7为NbSe2六方片的线性扫描伏安特性(LSV)曲线图，图中表明NbSe2六方片在-10mA·cm-2的电流密度下可实现255mV的过电势，表明NbSe2六方片有良好的析氢催化活性。
图8为NbSe2六方片的塔菲尔(Tafel)曲线图，图中塔菲尔斜率可以表示出电子转移速率的优劣，揭示HER动力学过程的作用机制。如图所示，NbSe2六方片的Tafel斜率为145mV·dec-1，表明NbSe2六方片中电子转移速率较快。
图9为NbSe2六方片的奈奎斯特(Nyquist)图，等效电路拟合结果显示图形以半圆为主，半圆直径代表了催化剂电极与电解液之间界面的电荷转移电阻(Rct)，其中电荷转移电阻Rct为220Ω。
以上所述的实施例仅对本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。
Claims (4)
1.一种硒化铌六方片的制备方法，其特征在于：主要步骤如下：
(1)将铌粉、硒粉按照摩尔比为0.2:1的比例混合均匀并压制成片；
(2)将压制好的圆片置于水平式直流电弧等离子体放电装置内阴阳极之间，阴极为钨棒，阳极为石墨锅；
(3)在水冷系统和惰性气体氛围的保护下，洗气后将气压升至40-60kPa，设置反应电流为40-100A，起弧至反应完全，冷却钝化至室温后，可在石墨锅内收集到灰黑色NbSe2粉末；
(4)将制备的NbSe2六方片直接作为活性物质，获得低电荷转移电阻和高电子转移速率的析氢反应催化剂。
2.按照权利要求1所述的硒化铌六方片的制备方法，其特征在于，所述放电过程中，向水冷系统通入循环冷却水。
3.按照权利要求1所述的硒化铌六方片的制备方法，其特征在于，所述铌粉、硒粉、惰性气体的纯度都保持在99.99％以上。
4.根据权利要求1-3任一所述的制备方法制得的NbSe2六方片催化剂，在析氢反应中的应用，其特征在于，所述NbSe2六方片析氢催化剂采用直流电弧等离子体放电装置直接获得。
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