CN111592361B - 一种氮化物高熵陶瓷纤维及其制备方法和应用 - Google Patents

一种氮化物高熵陶瓷纤维及其制备方法和应用 Download PDF

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CN111592361B
CN111592361B CN202010273050.2A CN202010273050A CN111592361B CN 111592361 B CN111592361 B CN 111592361B CN 202010273050 A CN202010273050 A CN 202010273050A CN 111592361 B CN111592361 B CN 111592361B
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entropy ceramic
spinning
ceramic fiber
precursor
entropy
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CN111592361A (zh
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赵彤
李伟
叶丽
陈凤华
孙娅楠
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Institute of Chemistry CAS
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Priority to PCT/CN2020/127990 priority patent/WO2021203695A1/zh
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Abstract

本发明公开了一种氮化物高熵陶瓷纤维及其制备方法和应用，所述高熵陶瓷纤维含有Ti、Hf、Ta、Nb和Mo元素，所述氮化物高熵陶瓷纤维呈单一晶相，且其中各元素呈分子级的均匀分布。所述高熵陶瓷纤维的制备方法包括：将含有目标金属元素的碳化物高熵陶瓷前驱体、纺丝助剂和溶剂混合均匀制成前驱体纺丝溶液，再经过纺丝、排胶和氮化工序，制得氮化物高熵陶瓷纤维。所述氮化物高熵陶瓷纤维可应用于光催化二氧化碳制备甲烷的工艺中。

Description

一种氮化物高熵陶瓷纤维及其制备方法和应用
技术领域
本发明属于高熵陶瓷技术领域，具体地说，涉及一种氮化物高熵陶瓷纤维及其制备方法和应用。
背景技术
高熵陶瓷是一种由至少五种元素组成的，每种元素含量在5～35％的单一相固溶体陶瓷。到目前为止，人们对于高熵陶瓷的研究仍然比较少，目前高熵陶瓷的存在形式只有粉体，块体和涂层，对高熵陶瓷的性能研究也局限于少数几个领域。
氮化物高熵陶瓷是一种由至少五种金属元素和氮元素组成的单一晶型的陶瓷，目前研究主要集中于氮化物高熵陶瓷涂层和粉体的制备。2012年，罗马尼亚的V.Braic等人采用物理气相沉积的方法在不锈钢表面沉积了一层(TiZrNbHfTa)N涂层，使得表面的硬度提高到33GPa，相比于传统金属涂层，表面硬度提高了三倍以上(V.Braic,Alina Vladescu,Nanostructured multi-element(TiZrNbHfTa)N and(TiZrNbHfTa)C hard coatings,Surface&Coatings Technology,211(2012):117-121)，但物理气相沉积方法对设备要求较高，只能制备涂层这种单一的二维材料，应用范围受限；2018年，国内华东理工大学和美国田纳西大学，橡树岭国家实验室联合开发了一种制备高熵氮化物陶瓷粉体的方法，该方法采用金属氯化物和尿素为原料，在800℃制备了单一晶型的(VCrNbMoZr)N纳米粉体，该粉体在超级电容器方面显示出了潜在的应用价值(Tian Jin,Xiahan Sang,Mechanochemical-Assisted Synthesis of High-Entropy Metal Nitride via a Soft Urea Strategy,2018(30):1707512)，但粉体材料在制备器件方面存在易脱落，分散不均匀等问题。
纤维是一种一维材料，具有尺寸小，比表面积高等特点，由于维度的限制，相比于粉体，块体和涂层，其物理化学特性会发生明显的改变，在电子信息，能源催化等领域具有广泛的应用前景。
光催化是一种以紫外、可见光为光源，半导体为催化剂，催化有机污染物降解，催化水分解制氢，催化CO2转化等化学反应发生的过程。目前的光催化剂主要为粉体形式，和催化原料及产物难分离，难以回收重复利用。
而光催化纤维由于具有宏观的棉、布等形态，可以较为便捷的和催化原料及产物分离，有利于催化剂的回收及重复利用，因此光催化纤维成为目前光催化剂的热门发展领域。
目前还没有关于氮化物高熵陶瓷纤维的报道，更没有将氮化物高熵陶瓷应用于光催化领域的先例。
有鉴于此，特提出本发明。
发明内容
本发明要解决的技术问题在于克服现有技术的不足，提供一种氮化物高熵陶瓷纤维及其制备方法，采用气纺丝、静电纺丝或者甩丝法制备纤维原丝，原丝经排胶和氮化制备氮化物高熵陶瓷纤维。本发明克服了高熵氮化物陶瓷目前只能以粉体，块体和涂层形态存在的局限，将高熵陶瓷的存在形式拓展到了纤维领域，同时本发明将高熵陶瓷的应用范围拓展到了光催化领域。
为解决上述技术问题，本发明采用技术方案的基本构思是：
本发明提供了一种氮化物高熵陶瓷纤维，所述高熵陶瓷纤维含有Ti、Hf、Ta、Nb和Mo元素，所述氮化物高熵陶瓷纤维呈单一晶相，且其中各元素呈分子级的均匀分布。
本发明的进一步方案为：所述高熵陶瓷纤维中各金属元素物质的量均占金属元素总物质的量的5～35％；优选的，所述各金属元素的物质的量相同。
上述方案中，所述纤维为致密颗粒堆积结构，其表面光滑，且纤维的长径比不小于50。
本发明还提供了一种如上所述氮化物高熵陶瓷纤维的制备方法，所述制备方法包括：将含有目标金属元素的碳化物高熵陶瓷前驱体、纺丝助剂和溶剂混合均匀制成前驱体纺丝溶液，再经过纺丝、排胶和氮化工序，制得氮化物高熵陶瓷纤维；所述目标金属选自Ti、Hf、Ta、Nb和Mo元素。
根据上述制备方法，所述高熵陶瓷前驱体制备过程包括：
(1)获取金属醇盐络合物：向含有目标金属元素的金属醇盐M(OR)n中滴入络合剂，滴完继续搅拌0.1～5h制得金属醇盐络合物；
(2)共水解：选取依步骤(1)制得的包含不同金属元素的金属醇盐络合物，混合均匀后缓慢滴加水和一元醇的混合液，滴完回流1～5h，并常压蒸馏制得金属醇盐共聚物；
(3)制备前驱体：将步骤(2)制得的金属醇盐共聚物与烯丙基酚醛混合均匀，升温至50～90℃，反应0.5～4h，之后降温得到碳化物高熵陶瓷前驱体。
根据上述制备方法，所述前驱体纺丝溶液中，碳化物高熵陶瓷前驱体、纺丝助剂和溶剂的质量比为1:0.1～1:5～20，优选为1:0.2～0.5:5～10。
上述方案中，纺丝前驱体溶液的制备或混合可借助其他技术手段，包括但不限于搅拌、超声等。
根据上述制备方法，步骤(1)中所述金属醇盐和络合剂的摩尔比为1:(0.15～0.5)n；当金属醇盐中的M为Ti或Hf时，n为4；当金属醇盐中的M为Nb、Ta或Mo时，n为5；所述络合剂为乙酰丙酮和/或乙酰乙酸乙酯。
上述方案中，本发明的工作人员发现，对不同类型的金属元素在形成络合物的过程中反应活性存在差异，若以类似的比例添加络合剂，虽然可以形成络合物但在后续多种金属元素醇盐络合物的混合水解过程中，会由于络合剂加入量的差异产生反应平衡性的倾斜，导致无法形成分子均匀分布的前驱体。而采用本申请所提供的金属醇盐与络合剂比例，则可以克服上述问题，使后续水解形成稳定的体系，以利于形成高熵陶瓷纤维。
根据上述制备方法，步骤(2)中水与总金属的摩尔比为0.8～1.3:1，一元醇与水的质量比为3～8:1；所述一元醇选自甲醇、乙醇、异丙醇、正丙醇、正丁醇、异丁醇、乙二醇甲醚、乙二醇乙醚中的一种或几种。
上述方案中，本发明提供的醇与水的比例，是在考虑不同反应活性的金属醇盐混合的基础上得出的，使得多种金属醇盐在共水解时的反应活性趋于相近，从而得到各元素分子级均匀分布的前驱体。
根据上述制备方法，步骤(3)中金属醇盐共聚物中金属元素的总物质的量与烯丙基酚醛的质量之比为1mol:18～20g。
上述制备方法中，不同金属的摩尔质量不同，不便于按质量统一成同一范围，本发明在此处按金属醇盐共聚物中的金属总物质的量来计算，而烯丙基酚醛属于非均聚的聚合物，不适宜采用物质的量表示，因此采用物质的量与质量的比值进行表达。
根据上述制备方法，所述氮化包括：在氨气气氛下对排胶后的纤维进行氮化，氮化温度为600～1000℃，氮化时间为0.5～5h。
根据上述制备方法，所述纺丝助剂选自聚甲基丙烯酸甲酯、聚醋酸乙烯酯、聚乙烯醇缩丁醛、聚乙烯吡咯烷酮中一种或几种；所述溶剂选自乙醇、丙酮、正丙醇、乙二醇甲醚、N,N-二甲基甲酰胺中的一种或几种。
上述方案中，纺丝助剂有助于改善溶液的流变性，如粘度、分散均匀性和稳定性等，可采用本领域常见的纺丝助剂，优选采用聚甲基丙烯酸甲酯、聚醋酸乙烯酯、聚乙烯醇缩丁醛、聚乙烯吡咯烷酮中的一种或多种的混合，例如聚甲基丙烯酸甲酯与聚醋酸乙烯酯的任意比例混合，或者聚醋酸乙烯酯与聚乙烯醇缩丁醛的任意比例混合，或者聚乙烯醇缩丁醛与聚乙烯吡咯烷酮的任意比例混合。
上述方案中，所用的溶剂是任意的，选用的溶剂有益于原料的溶解和分散，优选乙醇、丙酮、正丙醇、乙二醇甲醚、叔丁基甲醚、N,N-二甲基甲酰胺中的一种或多种的混合。
根据上述制备方法，所述排胶包括：在惰性气氛中，以0.5～5℃/min的升温速率升温至到500～600℃，并保温2～4h。
上述方案中，所述惰性气氛选自氮气、氩气、氦气中的一种或几种的混合。
根据上述制备方法，所述纺丝选自气纺丝、静电纺丝或者甩丝中的一种。
上述方案中，所述纺丝优选采用气纺丝技术，气纺丝条件为：纺丝气压0.02～0.2MPa，进料速度10～60mL/h，接收距离10～50cm，进料速度优选为30～60mL/h；所述气纺丝的气源选自压缩空气，压缩氮气，压缩氩气中的一种或几种的混合。
上述方案中，所述纺丝优选采用静电纺丝技术，静电纺丝条件为：纺丝电压5～15kV，进料速度10～60mL/h，接收距离10～50cm，进料速度优选为30～60mL/h。
上述方案中，所述纺丝优选采用甩丝技术，甩丝纺丝条件为：喷丝头转速200～5000r/min，接受距离20～100cm。
本发明还提供了一种如上所述氮化物高熵陶瓷纤维在光催化二氧化碳制备甲烷中的应用。与现有氮化物高熵陶瓷的应用相比，本发明将氮化物高熵陶瓷制成纤维并应用于光催化领域，首次提出了将氮化物高熵陶瓷应用于光催化CO2制备CH4的工艺，所述氮化物高熵陶瓷纤维具有较高的催化活性，且催化剂与反应物产物易于分离。
采用上述技术方案后，本发明与现有技术相比具有以下有益效果：
1.本发明以含有Ti、Hf、Ta、Nb和Mo金属元素，各金属元素物质的量均占总金属物质的量5～35％的碳化物高熵陶瓷聚合物前驱体为金属源，以气纺丝、静电纺丝或甩丝为成型手段，制备了氮化物高熵陶瓷纤维，所述纤维具有直径均匀，比表面积高等特点，拓展了氮化物高熵陶瓷的存在形式；
2.本发明所提供的的高熵陶瓷前驱体纺丝溶液具有流变性可调的特点，提高了纺丝性能的同时，还可使纺丝溶液在室温条件下密闭存储3周以上，粘度变化率不超过5％，降低了对后续工序(纺丝、排胶、氮化)的限制，进一步提高了纺丝效率；
3.本发明采用气纺丝、静电纺丝或甩丝方法制备高熵陶瓷纤维，设备简单，操作方便，成本低廉，可以得到平均直径可控的连续纤维棉或纤维无纺布，并可实现快速放大生产；
4.本发明制备的高熵氮化物纤维在光催化CO2转化制备CH4方面具有转化效率高，无需添加助催化剂，催化剂与原料产物易分离等特点，为氮化物高熵陶瓷首次应用于该领域，为氮化物高熵陶瓷的应用探索了新的发展方向。
下面结合附图对本发明的具体实施方式作进一步详细的描述。
附图说明
附图作为本发明的一部分，用来提供对本发明的进一步的理解，本发明的示意性实施例及其说明用于解释本发明，但不构成对本发明的不当限定。显然，下面描述中的附图仅仅是一些实施例，对于本领域普通技术人员来说，在不付出创造性劳动的前提下，还可以根据这些附图获得其他附图。在附图中：
图1是本发明实施例2得到的纤维XRD图；
图2是本发明实施例3得到的纤维XRD图；
图3是本发明实施例4得到的纤维XRD图；
图4是本发明实施例2得到的纤维SEM图；
图5是本发明实施例3得到的纤维EDS图；
图6是本发明实施例4制得纤维的实物图；
图7是本发明实施例13光催化反应后的气相色谱图。
需要说明的是，这些附图和文字描述并不旨在以任何方式限制本发明的构思范围，而是通过参考特定实施例为本领域技术人员说明本发明的概念。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对实施例中的技术方案进行清楚、完整地描述，以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1
本实施例提供了高熵陶瓷前驱体的通用制备方法，具体如下：
(1)获取金属醇盐：选取含有不同种类元素的过渡金属醇盐，当金属醇盐中的M为Hf、Nb、Ta或Mo时，所述醇盐按如下方法制备：将金属盐MCln或M(NO3)n分散在溶剂中，在-10～5℃条件下滴入一元醇，随后滴入三乙胺，滴加完毕后加热回流1～5h，过滤得到金属醇盐溶液；其中，金属盐、一元醇和三乙胺的比例为1：(1～2)n：(1～1.5)n；所述溶剂为正己烷、正庚烷、甲苯、二甲苯、乙二醇二甲醚、乙二醇二乙醚、叔丁基甲醚中的一种或几种；所述一元醇选自甲醇、乙醇、异丙醇、正丙醇、正丁醇、异丁醇、乙二醇甲醚、乙二醇乙醚中的一种或几种；
(2)制备金属醇盐络合物：在室温～80℃的条件下，向步骤(1)选取的金属醇盐M(OR)n中滴入络合剂，滴完继续搅拌0.1～5h制得金属醇盐络合物，所述金属醇盐和络合剂的摩尔比为1:(0.15～0.5)n；当金属醇盐中的M为Ti或Hf时，n为4；当金属醇盐中的M为Nb、Ta或Mo时，n为5；所述络合剂为乙酰丙酮或乙酰乙酸乙酯中的一种或两种的组合；
(3)共水解：选取依步骤(2)制得的包含不同金属元素的金属醇盐络合物，混合均匀后，在室温～90℃条件下缓慢滴加水和一元醇的混合液，其中水与总金属的摩尔比为0.8～1.3:1，一元醇与水的质量比为3～8:1，滴完回流1～5h，并常压蒸馏制得金属醇盐共聚物；所述一元醇选自甲醇、乙醇、异丙醇、正丙醇、正丁醇、异丁醇、乙二醇甲醚、乙二醇乙醚中的一种或几种；
(4)制备前驱体：将步骤(3)制得的金属醇盐共聚物与烯丙基酚醛混合均匀，其中金属元素总物质的量和烯丙基酚醛的质量之比为1mol:18～20g，升温至50～90℃，反应0.5～4h，之后降温得到碳化物高熵陶瓷前驱体。
为了更好地说明上述制备方法，本实施例还提供了一种具体的碳化物高熵陶瓷前驱体制备方法，其制备过程如下：
(1)获取金属醇盐：获取金属醇盐Hf(Oi-Pr)4、Ti(OPr)4、Ta(OCH2CH2OCH3)5、Mo(OCH2CH2OCH2CH3)5和Nb(OPr)5，其中Mo(OCH2CH2OCH2CH3)5，Hf(Oi-Pr)4，Ta(OCH2CH2OCH3)5和Nb(OPr)5是将金属盐MoCl5、HfCl4、TaCl5、和Nb(OPr)5分别分散在正庚烷中，-10～5℃下，分别滴入乙二醇乙醚、一元醇异丙醇、乙二醇甲醚、一元醇正丙醇，随后分别滴入三乙胺，滴加完毕后加热回流1～2h，分别过滤得到金属醇盐溶液；其中，金属盐、一元醇和三乙胺的比例分别为1:6:5、1:4:4、1:10:6、1:6:6；；
(2)制备金属醇盐络合物：在50℃条件下，分别向金属醇盐Hf(Oi-Pr)4、Ti(OPr)4、Ta(OCH2CH2OCH3)5、Mo(OCH2CH2OCH2CH3)5和Nb(OPr)5中滴入乙酰丙酮，滴完继续搅拌1h；金属醇盐Hf(Oi-Pr)4、Ti(OPr)4、Ta(OCH2CH2OCH3)5、Mo(OCH2CH2OCH2CH3)5及Nb(OPr)5和乙酰丙酮的摩尔比分别为1:1.1、1:0.8、1:1、1:2和1:1.5；
(3)共水解：将步骤(2)中所得的金属醇盐络合物，按等金属摩尔比混合均匀，70℃，向体系中缓慢滴加水和正丙醇的混合溶液，其中水与总金属的摩尔比为1.2:1，正丙醇与水的质量比为8:1，滴完回流2h；常压蒸馏得到金属醇盐共聚物；
(4)制备前驱体：将步骤(3)所得的金属醇盐共聚物与烯丙基酚醛混合均匀，醇盐共聚物中金属元素的总物质的量与烯丙基酚醛的质量之比为1mol:19.5g，升温至80℃，反应1h，降温得到碳化物高熵陶瓷聚合物前驱体。
实施例2
本实施例采用如下方法制备氮化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚乙烯吡咯烷酮10g，乙醇150g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：以压缩空气为气源，采用气流纺丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，纺丝气压为0.09MPa，进料速度为30mL/h，接收距离为40cm；
(3)排胶：将步骤(2)中收集到的纳米纤维棉置于热处理装置中，在氮气气氛下，以1℃/min的升温速率，升温到600℃，保温2h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为800℃，时间为2h，得到氮化物高熵纤维棉。
所述氮化物高熵陶瓷纤维的XRD如图1所示，SEM如图4所示。
实施例3
本实施例采用如下方法制备氮化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚乙烯醇缩丁醛10g，正丙醇285g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：以压缩氮气为气源，采用气流纺丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，纺丝气压为0.06MPa，进料速度为30mL/h，接收距离为40cm；
(3)排胶：将步骤(2)中收集到的纳米纤维棉置于热处理装置中，在氩气气氛下，以1.5℃/min的升温速率，升温到600℃，保温2h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为900℃，时间为2h，得到氮化物高熵纤维棉。
所述氮化物高熵陶瓷纤维的XRD如图2所示，EDS如图5所示。
实施例4
本实施例采用如下方法制备氮化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚醋酸乙烯酯10g，乙醇290g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：采用静电纺丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，纺丝电压为10kV，进料速度为40mL/h，接收距离为40cm；
(3)排胶：将步骤(2)中收集到的纳米纤维棉置于热处理装置中，在氩气气氛下，以1℃/min的升温速率，升温到600℃，保温2h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为1000℃，时间为2h，得到氮化物高熵纤维棉。
所述氮化物高熵陶瓷纤维的XRD如图3所示，实物如图6所示。
实施例5
本实施例采用如下方法制备氮化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚甲基丙烯酸甲酯10g，乙二醇甲醚300g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：采用静电纺丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，纺丝电压为15kV，进料速度为30mL/h，接收距离为45cm；
(3)排胶：将步骤(2)中收集到的纳米纤维棉置于热处理装置中，在氩气气氛下，以1.5℃/min的升温速率，升温到600℃，保温2h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为800℃，时间为2h，得到氮化物高熵纤维棉。
实施例6
本实施例采用如下方法制备氮化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚醋酸乙烯酯10g，乙醇290g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：采用甩丝装置将步骤(1)得到的前驱体溶液拉伸为纤维，纺丝头转速为1000r/min,接收距离为30cm；
(3)排胶：将步骤(2)中收集到的纳米纤维棉置于热处理装置中，在氩气气氛下，以1℃/min的升温速率，升温到600℃，保温2h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为1000℃，时间为2h，得到氮化物高熵纤维棉。
实施例7
本实施例采用如下方法制备碳化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚乙烯醇缩丁醛2g，聚乙烯吡咯烷酮10g，N,N-二甲基甲酰胺600g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：以压缩氩气为气源，采用气流纺丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，纺丝气压为0.02MPa，进料速度为10mL/h，接收距离为10cm；
(3)排胶：将步骤(2)中收集到的纳米纤维棉置于热处理装置中，在氮气气氛下，以0.5℃/min的升温速率，升温到550℃，保温4h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为600℃，时间为0.5h，得到氮化物高熵纤维棉。
实施例8
本实施例采用如下方法制备碳化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚醋酸乙烯酯8g，聚乙烯醇缩丁醛7g，正丙醇185g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：以压缩氮气为气源，采用气流纺丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，纺丝气压为0.2MPa，进料速度为60mL/h，接收距离为50cm；
(3)排胶：将步骤(2)中收集到的纳米纤维棉置于热处理装置中，在氩气气氛下，以3.5℃/min的升温速率，升温到600℃，保温3h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为700℃，时间为5h，得到氮化物高熵纤维棉。
实施例9
本实施例采用如下方法制备碳化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚甲基丙烯酸甲酯2g，聚醋酸乙烯酯1g，乙醇160g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：采用静电纺丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，纺丝电压为5kV，进料速度为10mL/h，接收距离为10cm；
(3)排胶：将步骤(2)中收集到的纳米纤维棉置于热处理装置中，在氮气气氛下，以1.5℃/min的升温速率，升温到500℃，保温2h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为1000℃，时间为2.5h，得到氮化物高熵纤维棉。
实施例10
本实施例采用如下方法制备碳化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚甲基丙烯酸甲酯15g，乙醇10g，乙二醇甲醚270g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：采用静电纺丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，纺丝电压为10kV，进料速度为60mL/h，接收距离为50cm；
(3)排胶：将步骤(2)中收集到的纳米纤维置于热处理装置中，在氦气气氛下，以2℃/min的升温速率，升温到600℃，保温3h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为800℃，时间为2h，得到氮化物高熵纤维棉。
实施例11
本实施例采用如下方法制备碳化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚乙烯醇缩丁醛10g，正丙醇130g，丙酮60g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：采用甩丝装置将步骤(1)得到的前驱体溶液拉伸为纤维，纺丝头转速为500r/min,接收距离为20cm；
(3)排胶：将步骤(2)中收集到的纳米纤维置于热处理装置中，在氮气气氛下，以1.5℃/min的升温速率，升温到600℃，保温2h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为900℃，时间为2h，得到氮化物高熵纤维棉。
实施例12
本实施例采用如下方法制备碳化物高熵陶瓷纤维：
(1)可纺性前驱体溶液的配制：采用实施例1记载的方法制备含有Ti、Hf、Ta、Nb、Mo的碳化物高熵陶瓷前驱体，取所述高熵陶瓷前驱体30g，聚乙烯醇缩丁醛10g，乙二醇甲醚190g，混合搅拌得到棕褐色均匀溶液；
(2)纺丝与收集：采用甩丝装置将步骤(1)得到的前驱体溶液拉伸为纳米纤维，喷丝头转速为5000r/min，接收距离为100cm；
(3)排胶：将步骤(2)中收集到的纳米纤维置于热处理装置中，在N2气氛下，以2℃/min的升温速率，升温到600℃，保温2h，得到排胶纤维；
(4)氮化：将步骤(3)所制备的排胶纤维置于热处理装置中，在氨气气氛下氮化，氮化温度为1000℃，时间为2h，得到氮化物高熵纤维棉。
实施例13
本实施例主要是为了说明本发明所制备氮化物高熵陶瓷纤维的催化效果。在CO2制备CH4的工艺中，以纯水和纯净的二氧化碳气体为原料，以实施例1中制备得到的高熵氮化物陶瓷纳米纤维棉为催化剂，在300W Xe灯照射的条件下进行光催化反应，反应12h后对反应容器中的气体进行气相色谱检测，发现有二氧化碳转化产物生成，且主要产物为甲烷，表明该催化剂具有较高的催化选择性。气相色谱如图7所示，出峰位置在0.777的为生成的H2，在2.543的为生成的CO，在4.685的为生成的CH4，可看出光催化产物主要为CH4，催化选择性在90％以上。
本发明的其他实施例通过测试也具有如上所述的催化效果。
以上所述仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专利的技术人员在不脱离本发明技术方案范围内，当可利用上述提示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明方案的范围内。

Claims (10)

1.一种氮化物高熵陶瓷纤维，其特征在于，所述高熵陶瓷纤维含有Ti、Hf、Ta、Nb和Mo元素，所述氮化物高熵陶瓷纤维呈单一晶相，各金属元素物质的量均占金属元素总物质的量的5～35%，且其中各元素呈分子级的均匀分布。
2.根据权利要求1所述的氮化物高熵陶瓷纤维，其特征在于，所述高熵陶瓷纤维中各金属元素的物质的量相同。
3.一种如权利要求1或2所述氮化物高熵陶瓷纤维的制备方法，其特征在于，所述制备方法包括：
将Ti、Hf、Ta、Nb和Mo元素的碳化物高熵陶瓷前驱体、纺丝助剂和溶剂混合均匀制成前驱体纺丝溶液，再经过纺丝、排胶和氮化工序，制得氮化物高熵陶瓷纤维；
所述高熵陶瓷前驱体是由如下方法制备的：
(1) 获取金属醇盐络合物：向含有目标金属元素的金属醇盐M(OR)n中滴入络合剂，滴完继续搅拌0.1～5 h制得金属醇盐络合物；
(2) 共水解：选取依步骤(1)制得的包含不同金属元素的金属醇盐络合物，混合均匀后缓慢滴加水和一元醇的混合液，滴完回流1～5h，并常压蒸馏制得金属醇盐共聚物；
(3) 制备前驱体：将步骤(2)制得的金属醇盐共聚物与烯丙基酚醛混合均匀，升温至50～90℃，反应0.5～4h，之后降温得到碳化物高熵陶瓷前驱体；
步骤(1)中所述金属醇盐和络合剂的摩尔比为1: (0.15～0.5) n; 当金属醇盐中的M为Ti或Hf时，n为4；当金属醇盐中的M为Nb、Ta或Mo时，n为5；
步骤(2)中水与总金属的摩尔比为0.8～1.3:1。
4.根据权利要求3所述氮化物高熵陶瓷纤维的制备方法，其特征在于，所述前驱体纺丝溶液中，碳化物高熵陶瓷前驱体、纺丝助剂和溶剂的质量比为1:0.1～1:5～20。
5.根据权利要求4所述氮化物高熵陶瓷纤维的制备方法，其特征在于，所述前驱体纺丝溶液中，碳化物高熵陶瓷前驱体、纺丝助剂和溶剂的质量比为1:0.2～0.5:5～10。
6. 根据权利要求3所述氮化物高熵陶瓷纤维的制备方法，其特征在于，所述氮化包括：在氨气气氛下对排胶后的纤维进行氮化，氮化温度为600～1000℃，氮化时间为0.5～5 h。
7.根据权利要求3所述氮化物高熵陶瓷纤维的制备方法，其特征在于，所述纺丝助剂选自聚甲基丙烯酸甲酯、聚醋酸乙烯酯、聚乙烯醇缩丁醛、聚乙烯吡咯烷酮中一种或几种；所述溶剂选自乙醇、丙酮、正丙醇、乙二醇甲醚、N,N-二甲基甲酰胺中的一种或几种。
8. 根据权利要求3或6所述氮化物高熵陶瓷纤维的制备方法，其特征在于，所述排胶包括：在惰性气氛中，以0.5～5℃/min的升温速率升温至到500～600℃，并保温2～4 h。
9.根据权利要求3所述氮化物高熵陶瓷纤维的制备方法，其特征在于，所述纺丝选自气纺丝、静电纺丝或者甩丝中的一种。
10.一种如权利要求1或2所述氮化物高熵陶瓷纤维在光催化二氧化碳制备甲烷中的应用。
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CN111592361B (zh) * 2020-04-09 2021-08-03 中国科学院化学研究所 一种氮化物高熵陶瓷纤维及其制备方法和应用
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CN113135755B (zh) * 2021-04-14 2023-03-17 厦门稀土材料研究所 一种柔性铈酸稀土高熵纳米纤维陶瓷膜及其制备方法和应用
CN113307632B (zh) * 2021-05-26 2022-04-12 山东大学 一种氧化物高熵陶瓷纤维的制备方法
CN114262813B (zh) * 2021-12-27 2022-05-20 安徽工业大学 一种内生纳米高熵碳化物增强高熵合金基复合材料及其制备方法
CN114804887A (zh) * 2022-03-22 2022-07-29 武汉科技大学 一种(CoCrFeMnNi)N高熵陶瓷粉体及其制备方法
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CN114843493A (zh) * 2022-05-23 2022-08-02 合肥精创科技有限公司 一种一维高熵氧化物纳米材料及其制备方法和应用
CN115572880B (zh) * 2022-09-23 2023-06-16 华南理工大学 高熵金属烯及其制备方法和应用
CN115611242B (zh) * 2022-10-08 2024-02-02 武汉理工大学 一种难熔金属高熵氮化物粉体及其制备方法
CN116237214B (zh) * 2022-12-13 2024-01-26 中国科学院合肥物质科学研究院 一种Al-Y-Cr-Fe-Er-O高熵复合氧化物阻氢涂层及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889836A (en) * 1988-02-22 1989-12-26 Gte Laboratories Incorporated Titanium diboride-based composite articles with improved fracture toughness
CN104988604A (zh) * 2015-07-31 2015-10-21 西安理工大学 一种碳化锆微纳米纤维的制备方法
CN105671392A (zh) * 2014-11-19 2016-06-15 北京科技大学 一种氮强化的TiZrHfNb基高熵合金及其制备方法
CN107266077A (zh) * 2016-04-08 2017-10-20 中国科学院化学研究所 一种超细碳化锆陶瓷纤维及其制备方法
CN110590372A (zh) * 2019-10-14 2019-12-20 石家庄铁道大学 一种过渡金属碳氮化物高熵陶瓷及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020165332A1 (en) * 1999-06-03 2002-11-07 Pope Edward J. A. Preceramic polymers to hafnium carbide and hafnium nitride ceramic fibers and matrices
JP2007061698A (ja) * 2005-08-30 2007-03-15 Hitachi Ltd 燃料電池用電極触媒、膜／電極接合体、燃料電池および携帯用電子機器
CN105671406A (zh) * 2016-02-19 2016-06-15 中原工学院 一种pcbn专用氮化物基高熵合金陶瓷结合剂
CN108786887A (zh) * 2018-06-20 2018-11-13 上海电力学院 一种用于光催化水分解制氢的催化剂及制备方法
CN111592361B (zh) * 2020-04-09 2021-08-03 中国科学院化学研究所 一种氮化物高熵陶瓷纤维及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889836A (en) * 1988-02-22 1989-12-26 Gte Laboratories Incorporated Titanium diboride-based composite articles with improved fracture toughness
CN105671392A (zh) * 2014-11-19 2016-06-15 北京科技大学 一种氮强化的TiZrHfNb基高熵合金及其制备方法
CN104988604A (zh) * 2015-07-31 2015-10-21 西安理工大学 一种碳化锆微纳米纤维的制备方法
CN107266077A (zh) * 2016-04-08 2017-10-20 中国科学院化学研究所 一种超细碳化锆陶瓷纤维及其制备方法
CN110590372A (zh) * 2019-10-14 2019-12-20 石家庄铁道大学 一种过渡金属碳氮化物高熵陶瓷及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis,characterization and microstructure of tantalum carbide-based ceramics by liquid polymeric precursor method;Yan Lu et al;《Ceramics International》;20150617;第12475-12479页 *

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