CN112054218B - 一种S修饰氧空位限域RuC纳米材料、其制备方法及应用 - Google Patents
一种S修饰氧空位限域RuC纳米材料、其制备方法及应用 Download PDFInfo
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Abstract
本发明公开一种S修饰氧空位限域RuC纳米材料、其制备方法及应用，从而在所有pH值下均能获得有效的多组分双功能催化剂。将氮源、硫源、贵金属氯化钌加入去离子水中，超声处理；所述氮源为三聚氰胺或尿素，所述硫源为N‑乙酰‑L‑半胱氨酸、L‑半胱氨酸、硫粉、硫代硫酸钠或过硫酸钠；将所得产物进行搅拌；干燥；将产物在研钵中研磨，待产物与三聚氰胺白色粉末完全融合后成黑灰色粉末；在保护气体下升温到550‑1000℃，碳化120－240 min，然后自然冷却至室温，水洗、干燥，即得S修饰氧空位限域纳RuC纳米材料。本发明为构筑有效的多级次空间结构和多功能催化剂提供科学、可行的制备工艺和设计思路。
Description
技术领域
本发明属于无机纳米材料化学及电化学领域，具体涉及一种S修饰氧空位限域RuC纳米材料、其制备方法及应用。
背景技术
为了解决以化石燃料为基础的能源相关的严重问题，迫切需要开发清洁和可再生能源替代品。在这方面，由于氢的高质量能量密度和无污染的性质，其被广泛认为是最有前途的清洁能源之一。生产纯氢最有希望的生态友好和经济方式是通过电化学水分解。电催化水分解是用于工业级高效氢气生成的廉价，清洁，可靠，稳定且负担得起的技术之一。在酸性和碱性电解液中，基于Pt的催化剂对于水电解中的析氢反应（HER）最有效。考虑到Pt的高价和不令人满意的效率，迫切需要低成本，高效且稳定的HER电催化剂来代替Pt。最近的努力集中在设计与商业Pt相比具有更高活性和耐久性的新型催化剂。
最近研究发现：贵金属钌（Ru）经济优势（Ru比Pt便宜约3倍），出色的活性和催化剂的长期性能稳定性使其成为有前途的HER替代催化剂。众所周知，HER效率与催化剂表面的金属氢键（MH）的强度以及氢还原所需的超电势密切相关。Ru-H键的吉布斯自由能（ΔGH）与HER火山图中心的最佳Pt-H键的吉布斯自由能非常接近。但是，即使Ru具有较高的电化学HER活性，它也很容易结块，因为它具有比Pt40大得多的内聚能。
如何均匀分散纳米颗粒进行了基底的研究，对于碳基质的研究开展较多，主要因为对于多孔碳材料的设计和制备中引入杂原子（氮、磷、硼等）之后，会改变电子结构和表面特性，从而增加其电化学活性。同时能赋予纳米颗粒在碳基质上的均匀性，使活性部分分散，很好的保护活性位点，催化剂就可以在其碳基的保护下保持较好的循环稳定性寿命。如何使纳米颗粒稳定性存在在碳基质上是设计高稳定性催化剂的关键。对于碳基质来说，多孔多缺陷位点是催化剂性能提高的关键，但是这些合成方法大多数涉及等离子体技术，氢氧化钾（KOH）蚀刻，基于模板的碳化以及通过N掺杂相减进行边缘重构，但是难以控制某些类型缺陷的综合，只能产生“随机”缺陷， 所以，非常需要开发一种简单，便宜并且易于扩展的方法。
最近Li等人（Li W, Liu Y., et al, Adv Mater, 2018, 30, 1800676）报道了所制备的催化剂，通过将钌纳米颗粒装载到新型碳中，表现出优异的催化性能，过电势为0mV，Tafel斜率为12 mV dec -1，在1 M KOH中具有出色的耐久性。另外，Ping和Chen等人（LuB, Guo L., et al, Nat Commun, 2019, 10, 631）制备了原子分散在多孔碳中的钌催化剂，该催化剂的催化性能明显优于商品铂催化剂。仅在12 mV的超电势下达到1 M KOH中10mV cm -2的电流密度和0.1 M KOH中47 mV的电流密度。开发高活性，选择性和低成本，操作简单，稳定性高的新型多功能催化剂在电化学能源的转换和存储中具有重要的理论以及广阔的前景。
发明内容
本发明目的在于提供一种S修饰氧空位限域RuC纳米材料、其制备方法及应用。
为实现上述目的，本发明采用如下技术方案：
一种S修饰氧空位限域RuC纳米材料的制备方法，其包括如下步骤：
1）制备N、S掺杂多孔碳纳米片：将三聚氰胺加入去离子水中，于60-80℃搅拌反应30-60min，然后加入硫源；超声处理45-60min，60~100℃干燥，即得；
2）N、S掺杂多孔碳纳米片与贵金属Ru进行共组装：取2.5－5g步骤1）所得产物，超声分散于25-50 ml去离子水中，超声时间为30-60 min；然后加入0.01-0.02 g 三氯化钌；室温超声处理45-60min；将所得产物进行机械搅拌5 h ~10h； 60-80℃干燥12 h ~48h，干燥产物在保护气体下升温至550-1000 ℃碳化100 min -240min，自然冷却至室温，离心、干燥即得S修饰氧空位限域RuC纳米材料。
具体的，步骤1）中，每5g三聚氰胺添加25-50ml去离子水进行搅拌。三聚氰胺指市售的C3H6N6，分子量 126.12。
步骤1）中，超声功率为10 kHz -40 kHz。所述硫源为N-乙酰-L-半胱氨酸、L-半胱氨酸、硫粉、硫代硫酸钠或过硫酸钠；以质量比计，硫源:三聚氰胺 = 1-8:100。
较好的，步骤2）中离心分离时，离心转速为6000-9000 rpm、离心时间为5-20 min。
较好的，步骤2）中，保护气体为氩气或氮气，保护气体的流量为50-100 sccm；碳化时，升温速率为5-10℃/min。
采用上述制备方法制备得到的S修饰氧空位限域RuC纳米材料。
上述S修饰氧空位限域RuC纳米材料作为HER催化剂，尤其是作为HER催化剂在提高锌空电池性能方面的应用。
与现有技术相比，本发明的有益效果体现在：
1）本发明提供了一种S修饰氧空位限域RuC纳米材料的制备方法，相比于等离子体技术、氢氧化钾（KOH）蚀刻、基于模板的碳化以及通过N掺杂相减进行边缘重构等方法，本发明方法不仅实现了在碳骨架内掺杂氮、硫双重元素，还实现了掺杂元素的数量可控，如通过控制加入三聚氰胺和硫化剂的量，可以实现氮、磷元素的含量可控。同时通过硫化级的掺杂量来控制空位缺陷的多少和类型，实现定向合成所需缺陷类型。
2）与借助二氧化硅、沸石等硬模板来构建多孔碳材料相比，本发明制备工艺简单，污染环境小，易于批量制备。同时，本发明获得的氮、硫共掺杂多孔纳米片具有优异的电化学性能。同时多级空间结构与纳米颗粒共组装，实现纳米颗粒和高活性单原子共同作用增加催化剂的多功能多方面的电化学储能性能。
3）本发明方法工艺简单，操作简便，后处理简单，成绩显著。
4）本发明采用三聚氰胺为前驱体，N乙酰L半胱氨酸为硫化剂，Ru纳米颗粒为主要活性点其在室温条件下可以直接合成，工艺简单、产率高，来源广泛，为大规模生产新型多功能电极材料提供了可能。
附图说明
图1：实施例1制备所得S修饰氧空位限域RuC纳米颗粒纳米片的SEM图；
图2：（a）为实施例2制备所得S修饰氧空位限域RuC纳米颗粒纳米片的TEM，(b)为HAADF-TEM高角度环形暗场-扫描透射电子显微镜表征图；
图3：（a）为实施例1制备所得S修饰氧空位限域RuC纳米颗粒纳米片的X射线衍射，（b）为实施例1的X射线光电子能谱图；
图4为实施例1制备所得S修饰氧空位限域RuC纳米颗粒纳米片的N2吸附脱附曲线（a）和实施例1的孔径分布图（b）；
图5：实施例1制备所得S修饰氧空位限域RuC纳米颗粒纳米片的电子自旋共振谱；
图6：为实施例1、对照例1、对照例2、实施例18和商业Pt/C用于酸性条件下电化学测试的极化曲线；
图7：实施例1、对照例1、对照例2、实施例18和商业Pt/C用于碱性条件下电化学测试的极化曲线；
图8：实施例1、对照例1、对照例2、实施例18和商业Pt/C用于中性条件下电化学测试的极化曲线；
图9中，（a）为实施例1用于酸性条件下循环测试的I-T曲线，（b）为实施例1用于碱性条件下循环稳定性测试的I-T曲线，（c）为实施例1用于中性条件下循环稳定性测试的I-T曲线；
图10中，（a）为实施例1用于液态锌空电池测试循环稳定性CP曲线，（b）为实施例1用于水解测试循环稳定性I-T曲线。
具体实施方式
以下结合实施例对本发明的技术方案作进一步地详细介绍，但本发明的保护范围并不局限于此。
实施例1
一种S修饰氧空位限域RuC纳米材料的制备方法，其包括如下步骤：
1）、制备N、S掺杂多孔碳纳米片：在100ml烧杯中，称取5g三聚氰胺，然加入50mL去离子水进行混合，于60℃搅拌反应30 min，然后加入0.15 gN-乙酰-L-半胱氨酸，超声处理60min（超声功率为20 kHz），80 ℃干燥至恒重，即得；
2）、取5g步骤1）所得产物，20 kHz超声分散于50 ml去离子水中，超声时间为30min，加入0.02 g 三氯化钌在功率20 kHz下超声处理60min；将所得产物在三口烧瓶中进行搅拌8 h，搅拌速率500 rpm；所得产物放置恒温干燥箱中80℃干燥24 h，将干燥产物在氮气气氛下(氮气气体的流量为60 sccm) 以5℃/min的升温速度升温至900℃碳化120 min，然后自然冷却至室温，将获得的黑色粉末放入离心管中，加入40mL去离子水进行离心，离心转速为6000 rpm、离心时间为15 min，离心后放入恒温干燥箱中在60℃下干燥24 h，即得S修饰氧空位限域RuC纳米材料。
对照例1
与实施例1的区别在于：不加硫源，即步骤1）中，N-乙酰-L-半胱氨酸的添加量为0g；其他步骤均同实施例1。
对照例2
与实施例1的区别在于：不加金属纳米颗粒Ru，即步骤2）中，氯化钌的添加量为0g；其他步骤均同实施例1。
不加金属源直接碳化得到的纳米片测试性能几乎没有HER性能，说明金属纳米颗粒对碳基质的改性有很大的作用。
实施例2
与实施例1的区别在于：步骤1)中，将三聚氰胺改为尿素；其他步骤均同实施例1。
实施例3-6
与实施例1的区别在于：步骤1)中，将N-乙酰-L-半胱氨酸改为L-半胱氨酸、硫粉、硫代硫酸钠和过硫酸钠；其他步骤均同实施例1。
实施例7-13
与实施例1的区别在于：步骤1)中，将N-乙酰L-半胱氨酸的量依次改为0.05 g、0.1g、0.2 g、0.25 g、0.3 g、0.35 g和0.4 g；其他步骤均同实施例1。
实施例14-15
与实施例1的区别在于：步骤2)中，将加入三氯化钌后搅拌的产物干燥时间依次改为12 h和48 h；其他步骤均同实施例1。
实施例16-20
与实施例1的区别在于：步骤2)中，将碳化温度依次分别改为550℃、600℃、700℃、800℃、1000℃；其他步骤均同实施例1。
实施例21-23
与实施例1的区别在于：步骤3)中，将碳化时间依次分别改为100 min、180 min和240 min；其他步骤均相同实施例1。
结构表征和性能测试
（一）结构表征
实施例1所得产物的扫描电镜SEM图见图1，透射电镜TEM图见图2中（a），高角度环形暗场-扫描透射电子显微镜表征HAADF-TEM图见图2中（b）。上述结果表明：采用三聚氰胺，N-乙酰-L-半胱氨酸和氯化钌为原料用软模板法所制备的产物为氮掺杂多孔碳纳米片（见图1）；所制备的目标产物的TEM图像清楚地表明，RuC纳米颗粒均匀地锚定在碳纳米片的表面上（见图2a），纳米颗粒的粒径分布在0.5-3.8 nm范围内，平均粒径为1.8 nm（见图2b）。X射线衍射XRD图见图3中（a），X射线光电子能谱XPS见图3中（b）图；说明所得材料证明了RuC纳米颗粒分散在碳基质中；比表面积和孔径分布测试(图4) 显示414.576 m2 g-1的相对高表面积以及3.8nm和36.8 nm的分级孔径，这表明它们具有独特的多孔结构和更活跃的位点暴露，这将提高传质效率并实现电催化剂的高利用率；电子自旋共振（ESR）曲线（图5）以检测顺磁信号，其 ≈3512 G（g = 2.0）的信号强度反映了未配对电子的不饱和浓度。这充分证实了由于S掺杂而形成的大量氧空位。S修饰O空位缺陷位点的暴露，更能稳定RuC纳米颗粒在碳基质上的存在，提高电化学稳定性。
（一）性能测试
分别把实施例1、对照例1、对照例2、实施例16制备的纳米材料作为催化剂加载到玻碳电极上作为工作电极，银氯化银电极作为参比电极，铂片电极为对电极，组装三电极体系测试HER析氢电化学测试的极化曲线，电解液为0.1 MKOH、0.5 MH2SO4和1 MPBS，扫描速率为5 mV s-1；与此同时，以商业Pt/C作为对照工作电极。工作电极的制备过程为：在超声处理下，将2.5 mg每个样品分散在由225μL异丙醇和25μL 5 wt%Nafion水溶液组成的溶液中，得到催化剂分散液。取8μL催化剂分散液，每次4μL逐滴加到玻碳电极上，在室温下干燥24 h用于不同pH的电解液HER析氢极化曲线见图6可以看出：与实施例1比较，对照例1的10 mA cm-2对应的和电压不如实施例1中加入硫源后样品的电压低，由此可以得出：采用硫元素制备S修饰的O空位缺陷具有较好的HER析氢性能。与实施例1比较，对照例2的10 mA cm-2对应的和电压不如实施例1加RuC纳米颗粒后样品的电压低，由此可以得出：将钌纳米颗粒装载到新型碳中，表现出优异的HER催化性能。与实施例1比较，实施例16表明在碳化温度在550 ℃下纳米片负载的RuC原子的HER性能远不如900℃碳化温度下的性能，主要是因为在温度逐渐升高时，三聚氰胺会发生分解，更多的C，N发生键合，部分缺陷N的生成，促进了RuC的纳米颗粒的稳定性能，有助于增强催化剂的活性。实施例1产物在不同电解液条件下的HER性能（图7，图8）表现出较好的电流密度和电压，在10 mA cm-2对应的电压分别为1M KOH为5 mV、0.5M H2SO4为89 mV和1M PBS为98 mV，与商业Pt/C性能相比具有较好的HER析氢性能。
为测试本发明实施例1产物在全PH条件下HER性能的稳定性测试见图9，经过长时间的I-T曲线HER析氢性能在全PH条件下具有较好的稳定性。可以看出材料在1M KOH，0.5MH2SO4，1MPBS电解液下，经过50 h的循环测试，都保持在75%以上的稳定性。本申请分别进行了锌空电池和水解的稳定性。其中锌空电池稳定性测试体系为6 M KOH电解液，使用干净的锌箔作为阳极，所制备的产物为工作电极，电极材料的制备方法与HER电极材料制备一致，负载量为2.5 mgcm-2。在恒定电压下，所制备实施例1产物的锌空电池具有较好的稳定性见图10中（a）。图10中（b）不同电解液条件下的条件下的I-T曲线，经过10000s后，实施例1制得的电极材料具有较好的稳定性和活性。
以上实施案例仅用于说明本发明的优选实施方式，但本发明并不限于上述实施方式，在所述领域普通技术人员所具备的知识范围内，本发明的精神和原则之内所作的任何修改、等同替代及改进等，均应视为本申请的保护范围。
Claims (7)
1.一种S修饰氧空位限域Ru@C纳米材料的制备方法，其特征在于，包括如下步骤：
1）制备N、S掺杂多孔碳纳米片前驱体：将三聚氰胺加入去离子水中，于60-80℃搅拌反应30-60min，然后加入硫源；超声处理45-60min，60~100℃干燥，即得；硫源为N-乙酰-L-半胱氨酸，以质量比计，硫源:三聚氰胺 = 1-8:100；
2）N、S掺杂多孔碳纳米片与贵金属Ru进行共组装：取2.5－5g步骤1）所得产物，超声分散于25-50 ml去离子水中，超声时间为30-60 min；然后加入0.01-0.02 g 三氯化钌；室温超声处理45-60min；将所得产物进行机械搅拌5 h ~10h； 60-80℃干燥，干燥产物在保护气体下升温至550-1000 ℃碳化100 min -240 min，自然冷却至室温，离心、干燥即得S修饰氧空位限域Ru@ C纳米材料。
2.如权利要求1所述S修饰氧空位限域Ru@C纳米材料的制备方法，其特征在于，步骤1）中，每5g三聚氰胺添加25-50ml去离子水进行搅拌；超声功率为10 kHz -40 kHz。
3.如权利要求1所述S修饰氧空位限域Ru@C纳米材料的制备方法，其特征在于，步骤2）中，离心分离时，离心转速为6000-9000 rpm、离心时间为5-20 min。
4.如权利要求1所述S修饰氧空位限域Ru@C纳米材料的制备方法，其特征在于，步骤2）中，保护气体为氩气或氮气，保护气体的流量为50-100 sccm；碳化时，升温速率为5-10℃/min。
5.采用权利要求1至4任一所述方法制备得的S修饰氧空位限域Ru@C纳米材料。
6.权利要求5所述的S修饰氧空位限域Ru@C纳米材料在作为HER催化剂中的应用。
7.权利要求5所述的S修饰氧空位限域Ru@C纳米材料作为催化剂在提高锌空电池性能中的应用。
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