CN111468152A - 一种花状wc助催化剂制备及其应用 - Google Patents
一种花状wc助催化剂制备及其应用 Download PDFInfo
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Abstract
本发明涉及的是一种花状WC助催化剂的制备及其应用。该助催化剂的制备采用如下具体步骤:将表面活性剂聚乙烯吡咯烷酮(PVP)溶解、硝酸酸化,加入钨源超声分散后,水热,冷却,干燥,碳化,获得目的产物。本发明的优点是:制备条件温和,工艺简单,价格低廉,高温煅烧法直接合成了具有大比表面积的花状WC,该催化剂可应用于光催化产氢、电催化、光电催化产氢领域。
Description
技术领域
本发明涉及一种由层状堆积呈现花状的WC助催化剂制备及其应用。该助催化剂应用于光催化产氢助催化剂,展现出高效稳定的光催化产氢活性,也有望应用于气敏材料、催化剂载体或催化加氢脱氢领域。
背景技术
过渡金属氧化物微纳米材料具有光、电、磁等特性,因而其制备方法引起了科学家的关注。其中,三氧化钨具有光致变色、电致变色、气敏特性以及光降解等,可以被应用于传感器、锂电池的负极材料、超级电容器电极材料和光催化剂等领域。三氧化钨纳米粉体的制备方法有沉淀法、水热法、微乳液法等。而水热制备的三氧化钨具有特殊的形貌,因此我们选择加入表面活性剂调控三氧化钨的形貌从而进一步调控碳化钨的形貌特征。
过渡金属碳化物具有熔点高、硬度大、良好的热稳定性和机械稳定性、耐腐蚀等特点,主要用于机械切削、矿物开采、制造刀具钻具的材料以及核反应堆等领域。研究发现,过渡金属碳化物以及相应的复合物可以作为催化剂应用在催化加氢、脱氢、催化加氢脱硫脱氮、异构化、芳构化等领域,都具有催化作用。碳化钨的表面性质和催化活性接近于贵金属,因此被称为“类贵金属”。而商业碳化钨是块体的形态影响了碳化钨的催化效果。因此我们采用引入表面活性剂水热法制备花状结构的碳化钨,以此提高碳化钨的催化效果。
发明内容
本发明的目的是改进商业碳化钨催化效果低,应用受到局限的特点,提出了一个形貌可控、产量高、工艺流程简单、条件温和的WC纳米花制备方法。
本发明的技术方案
一种WC纳米花的制备方法,具体步骤如下:
(1)将0.5g聚乙烯吡咯烷酮(PVP)溶于55mL去离子水中,搅拌30min至固体溶解完全,得到饱和溶液;
(2)在步骤(1)的饱和溶液中逐滴加入5mL浓度为69wt%的硝酸酸化;在酸化的溶液中加入1.0g偏钨酸铵,溶液开始出现白色沉淀,超声25min后,溶液变成乳白色溶液;
(3)将步骤(2)的乳白色溶液转移到100mL水热釜里,再加入12mL H2O2,然后放入电热恒温鼓风干燥箱240oC水热12h,冷却后去除上清液获得黄色的沉淀物,分别用无水乙醇和去离子水离心洗涤3~5次,然后放入真空干燥箱中80oC~120oC烘干12~24h;
(4)将烘干后得到的黄色WO3研磨0.5~2h后转移到管式炉中,在流速为150mL/min的一氧化碳氛围中,950oC煅烧2~10h,升温速率为5~10oC/min,冷却后通入流速为30~80mL/min的惰性气体保持12~24h。
本发明的优点是:该制备方法工艺流程简单、条件温和、成本低和产量高,适用于大规模化生产,制备的WC呈现由片组装的纳米花。该助催化剂可应用于光催化产氢领域,也有望广泛应用于气敏材料、催化剂载体或催化加氢脱氢领域。
附图说明
图1.WO3的XRD图。
图2.WO3碳化合成WC的XRD图。
图3.WO3的扫描电子显微镜(SEM)。
图4.WC的扫描电子显微镜(SEM)。
图5.WC的光催化产氢活性图。
图6.担载不同量WC的光催化产氢活性图。
具体实施方式
下面通过具体的实施例对本发明作进一步详细说明。
实施例1一种具有片层组装呈现纳米花状结构的WC助催化剂的制备方法,步骤如下:
(1)将0.5g聚乙烯吡咯烷酮(PVP)溶于55mL去离子水中,搅拌30min至固体溶解完全,得到饱和溶液;在饱和溶液中以1mL/min的滴速逐滴加入5mL浓度为69wt%的硝酸酸化,并一直磁力搅拌,搅速为800rpm/min;在酸化的溶液中加入1.0g偏钨酸铵,溶液开始出现白色沉淀,超声25min后,溶液变成乳白色溶液;随后转移到100mL水热釜里,再加入12mL H2O2,放入电热恒温鼓风干燥箱240oC水热12h,冷却至室温后去除上清液获得黄色的沉淀物,分别用无水乙醇和去离子水离心洗涤3次,然后放入真空干燥箱中80oC,12h烘干,取出研磨即得黄色的粉末WO3。
(2)取0.5g的WO3放入石英舟转移到管式炉中,在流速为100mL/min的一氧化碳氛围中,从室温至煅烧碳化的升温速率为5oC/min,950oC煅烧2h,冷却至室温后通入流速为40mL/min的体积比99:1的N2:O2气氛保持12h。即可制得PVP辅助合成的黑色粉末WC。
(3)将0.1g的WC分散在50mL硝酸镉溶液,搅拌20分钟后,逐滴加入60mL 14mol/L硫化钠水溶液,待滴加结束后继续搅拌60分钟,后陈化8小时,转移到100mL的水热釜中180oC保持24小时,冷却至室温过滤并用去离子水和无水乙醇洗涤三次,转移到真空干燥箱干燥12h,得到10%WC/CdS复合光催化剂。
催化剂的应用:
将上述制备的复合光催化剂WC/CdS取0.1g加入到100mL体积分数为10%的乳酸溶液,采用300W氙灯,电流为15mA,光照时间为1h,进行光催化分解水产氢反应。
实施例2
催化剂的制备参考实施例1,不同之处在于步骤(3)中将聚乙烯吡咯烷酮(PVP)辅助合成的WC取0.01g分散在50mL硝酸镉溶液,最终制得催化剂中WC的担载量为1.0%,其余步骤与实施例1相同。
实施例3
催化剂的制备参考实施例1,不同之处在于步骤(2)中将聚乙烯吡咯烷酮(PVP)辅助合成的WC取0.04g分散在50mL硝酸镉溶液,最终制得催化剂中WC的担载量为4.0%,其余步骤与实施例1相同。
实施例4
催化剂的制备参考实施例1,不同之处在于步骤(3)中将聚乙烯吡咯烷酮(PVP)辅助合成的WC取0.07g分散在50mL硝酸镉溶液,最终制得催化剂中WC的担载量为7.0%,其余步骤与实施例1相同。
实施例5
催化剂的制备参考实施例1,不同之处在于步骤(3)中将聚乙烯吡咯烷酮(PVP)辅助合成的WC取0.13g分散在50mL硝酸镉溶液,最终制得催化剂中WC的担载量为13.0%,其余步骤与实施例1相同。
实施例6
催化剂的制备参考实施例1,不同之处在于步骤(3)中将聚乙烯吡咯烷酮(PVP)辅助合成的WC取0.15g分散在50mL硝酸镉溶液,最终制得催化剂中WC的担载量为15.0%,其余步骤与实施例1相同。
对比例1
催化剂的制备参考实施例1,不同之处在于步骤(1)中不加入表面活性剂(PVP),最终制得未加表面活性剂辅助合成的WO3,
其余步骤与实施例1相同。
对比例2
催化剂的制备参考实施例1,不同之处在于步骤(2)中取0.5g未加表面活性剂辅助合成的WO3放入石英舟转移到管式炉中,最终制得未加表面活性剂辅助合成的WC,其余步骤与实施例1。
对比例3
催化剂的制备参考实施例1,不同之处在于步骤(3)中将未加表面活性剂辅助合成的WC取0.1g分散在50mL硝酸镉溶液,最终制得催化剂中未加表面活性剂辅助合成的WC的担载量为10.0%,其余步骤与实施例1。
对比例4
催化剂的制备参考实施例1,不同之处在于步骤(3)中将商业WC取0.1g分散在50mL硝酸镉溶液,最终制得催化剂中商业WC的担载量为10.0%,其余步骤与实施例1。
光催化产氢活性评价
将实施例1-6和对比例3-4所得光催化剂分别进行光催化产氢活性评价,如图5和图6所示。
由实施例1-6催化剂的光催化产氢活性对比可知,在同一反应条件下,当聚乙烯吡咯烷酮(PVP)辅助合成的WC的担载量增加时,光催化产氢活性分布呈现火山型,先增加后减少,WC的最佳担载量为10.0%,即10.0%WC/CdS的光催化产氢量最大,可以达到2451.27μmol/h。证明了聚乙烯吡咯烷酮(PVP)辅助合成的WC具有优异的助催化性能。
由对比例1-3催化剂的光催化产氢活性可知,在相同助催化剂WC的担载量下,选取担载量为10.0%,发现超出权利要求外的催化剂展现了低的光催化产氢活性。
图1是实施例1和对比例2在有无表面活性剂条件下制备不同种类WO3的XRD图,添加聚乙烯吡咯烷酮(PVP)后,合成的WO3归属于正交相WO3!0.33H2O(标准卡片PDF#35-0270),未添加表面活性剂合成的WO3归属于单斜相WO3(标准卡片PDF#43-1035),图2为实施例1和对比例3在不同前驱体WO3碳化后合成WC,以及商业WC的XRD图,这几种WC均归属于六方相WC(标准卡片PDF#51-0939)。
从图3是实施例1在添加聚乙烯吡咯烷酮(PVP)后,从SEM可以看出合成的WO3呈现出六方棒状,长度大约为8.1~22.5μm,厚度约为0.87~2.5μm。
图4是实施例1和对比例2分别制备的WC以及商业WC的SEM图,从图a和b中可以看出合成的WC呈现出由片层堆积的球状纳米花,纳米花的直径范围约为5~12.4μm,比表面积达到6.9457m2/g,单层片的平均厚度在2~10nm;图c和d可以看出未加表面活性剂合成的WC呈现出纳米片状,比表面积达到6.0045m2/g,纳米片的面积约为3.63~50.13μm2,单层片的平均厚度约为0.09~3.38μm;图e和f可以看出商业WC呈现出块状,比表面积达到1.97m2/g,块体的平均厚度约为39.55~207.7nm,块的面积约为0.01~0.3μm2。
Claims (8)
1.一种花状WC助催化剂的制备方法,其特征在于:以聚乙烯吡咯烷酮(PVP)和偏钨酸铵为原料,经水热合成前驱体WO3碳化制得由片层堆积的球形花状WC。
2.按照权利要求1所述的花状WC助催化剂的制备方法,其特征在于:具体过程为,将0.1~1.0g,优选0.2~0.8g;聚乙烯吡咯烷酮(PVP)加入25~60mL去离子水溶解后,优选范围35~55mL;加入0.1~1.5g偏钨酸铵,优选0.5~1.0g;出现白色沉淀后进行超声处理,随后将沉淀水热,洗涤,出现黄色的沉淀WO3,碳化后得到具有大比表面积的花状WC。
3.按照权利要求2所述的制备方法,其特征在于:出现白色沉淀后超声处理的时间为20~60min;再将上述溶液转移到水热釜里,按100mL水热釜计,加入5~20mL H2O2,优选12~15mL;然后放入电热恒温鼓风干燥箱进行水热,水热的温度为200~250℃,采用较优温度为240~245℃,水热时长为10~36h,优选12~16h;冷却至20~40℃后去除上清液,分别用无水乙醇和去离子水依次离心洗涤3~5次,黄色沉积物真空干燥,烘干温度60℃~100℃,优选90-95℃;烘干温度12~24h,优选18~20h;得WO3。
4.按照权利要求2所述的制备方法,其特征在于:花状WC的制备:将WO3研磨0.5~2h后转移到管式炉中碳化,在流速为60~150mL/min的一氧化碳氛围中,优选100~120mL/min;碳化的温度为850~1000℃,优选900℃,煅烧1.5~5h,优选2~3h,从室温至煅烧碳化的升温速率为2~10℃/min,优选5~6℃/min;碳化后冷却至20~40℃后通入流速为30~80mL/min,优选40~50mL/min;在惰性气氛下,体积比为98:2~99.5:0.5的N2:O2钝化气中钝化,优选99:1;保持12~24h,优选16~20小时。
5.一种权利要求1-4任一所述制备方法制备获得的WC。
6.一种权利要求5所述的WC作为催化剂的活性成份或载体可应用于光催化、电催化或光电催化产氢过程中。
7.如权利要求6所述的应用,其特征在于:
所述的WC作为催化剂的活性成份可应用于光催化分解水产氢。
8.根据权利要求7所述WC的应用,将权利要求7所述的WC与CdS半导体光催化剂复合,质量比范围为1:100~15:100,优选10:100~12:100,可用于光催化分解水制氢过程中。
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