CN114984960B - 基于阳离子掺杂的钴氧化物催化剂及其制备方法与应用 - Google Patents
基于阳离子掺杂的钴氧化物催化剂及其制备方法与应用 Download PDFInfo
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- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical group O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种基于阳离子掺杂的钴氧化物催化剂及其制备方法与应用。本发明所述基于阳离子掺杂的钴氧化物催化剂中的阳离子进入钴氧化物晶格提高了氧缺陷含量；所述阳离子为Mn、Ce、Fe阳离子中的至少一种。所述基于阳离子掺杂的钴氧化物催化剂还加入碳形成复合相，钴氧化物以纳米片形态分布于碳表面得到基于阳离子掺杂结合碳复合改性的钴氧化物催化剂。本发明的催化剂应用于甲醛催化氧化体系，兼具高本征性能和丰富的活性位点，可在100℃下高效且稳定地实现甲醛的完全催化分解，其活性优于多数目前报道的钴基非贵金属催化剂。
Description
技术领域
本发明属于催化材料技术领域，具体涉及一种基于阳离子掺杂的钴氧化物催化剂及其制备方法与应用。
背景技术
甲醛是常见的室内空气污染物，具有强烈的致癌作用，国际癌症研究机构已经将其认定为致癌物。因其具有与体内蛋白质等生物质发生反应而引起生物质变性的高化学反应活性，长期暴露于含有低浓度甲醛的环境中可对人体的感官、呼吸以及神经系统造成不良影响，甚至导致鼻咽癌和白血病等严重疾病，严重危害人类的身体健康。因此，研究开发安全高效的甲醛防治技术具有重要意义。在现有的众多除甲醛技术中，催化氧化法因具有去除效率高、环境友好等优点而被公认为最具应用前景的技术方案。发展安全高效的甲醛氧化催化剂是推进催化氧化消除甲醛技术实际应用的关键。
当前常用于甲醛催化氧化的催化剂主要有两类，负载型贵金属催化剂(Pt，Au，Pd和Ag等)和非贵金属催化剂(Co3O4，MnO2和CeO2等)。负载型贵金属催化剂具有优异的催化性能，但高昂的材料成本严重制约其实际应用。非贵金属催化剂廉价易得，但普遍存在低温活性过低的严重问题。从实用化角度，运用先进的成分调控与结构调制方法来提高非贵金属催化剂的催化活性是除甲醛技术发展的主流方向。根据文献报道，对非贵金属催化剂的改性主要集中于组分调制和结构优化，常采用掺杂和复合以及结构纳米化、形貌控制和缺陷调变等策略。但总体而言，非贵金属催化剂仍普遍存在活性偏低、长期工作稳定性和耐湿性欠佳等问题[J.Alloy.Compd.859(2021)157808]，因此发展高活性的非贵金属催化剂设计理念与可控合成方法仍是推进甲醛催化氧化技术实用化进程中亟待解决的关键问题。
发明内容
针对以上现有技术存在的缺点和不足，本发明的首要目的在于提供一种基于阳离子掺杂的钴氧化物催化剂。本发明催化剂具有纳米片形貌和富含氧空位的特征，兼具高本征催化活性和丰富的活性位点。
本发明的另一目的在于提供上述基于阳离子掺杂的钴氧化物催化剂的制备方法。本发明采用共沉淀结合热处理两步法，首先以含有水合硝酸金属盐水溶液为起始原料，采用共沉淀法制备得到羟基钴氧化物前躯体，然后经热处理得到具备阳离子掺杂的钴氧化物催化剂。该方法原料易得、操作简便、便于量产，使得工业化生产成为可能。
本发明的再一目的在于提供上述阳离子掺杂的钴氧化物催化剂在甲醛催化氧化中的应用，可在100℃下高效且稳定地催化甲醛氧化分解，其活性优于多数目前报道的钴基非贵金属催化剂。
最后本发明还提供了基于阳离子掺杂结合碳复合改性的钴氧化物催化剂，在上述基于阳离子掺杂的钴氧化物催化剂加入碳形成复合相得到；可在90℃下高效且稳定地催化甲醛氧化分解。
本发明目的通过以下技术方案实现：
一种基于阳离子掺杂的钴氧化物催化剂，所述基于阳离子掺杂的钴氧化物催化剂中的阳离子进入钴氧化物晶格提高了氧缺陷含量；所述阳离子为Mn、Ce、Fe阳离子中的至少一种。
优选的，所述基于阳离子掺杂的钴氧化物催化剂的化学式为CoxM3-xO4，其中2.25≤x＜3，M为Mn、Ce、Fe中的至少一种。
优选的，所述钴氧化物为四氧化三钴。
上述的基于阳离子掺杂的钴氧化物催化剂的制备方法，包括如下步骤：
将可溶性钴盐、可溶性金属盐、碱分散于去离子水中得分散液，搅拌后所得沉淀物经清洗、干燥、空气气氛下煅烧后制得基于阳离子掺杂的钴氧化物催化剂；所述可溶性金属盐中的金属为Mn、Ce、Fe中的至少一种，所述碱为氢氧化钠、氢氧化钾中的至少一种。
优选的，所述基于阳离子掺杂的钴氧化物催化剂还加入碳形成复合相，钴氧化物以纳米片形态分布于碳表面。
进一步优选的，所述碳为非晶碳。
进一步优选的，所述基于阳离子掺杂的钴氧化物催化剂的化学式为CoxM3-xO4/C，其中2.25≤x＜3，M为Mn、Ce、Fe中的至少一种；所述钴氧化物的纳米片为二十到一百纳米的横向尺寸和一到五纳米的厚度。
上述的基于阳离子掺杂的钴氧化物催化剂的制备方法，包括如下步骤：
将可溶性钴盐、可溶性金属盐、炭黑、碱分散于去离子水中得分散液，搅拌后所得沉淀物经清洗、干燥、空气气氛下煅烧后制得基于阳离子掺杂的钴氧化物催化剂；所述可溶性金属盐中的金属为Mn、Ce、Fe中的至少一种，所述碱为氢氧化钠、氢氧化钾中的至少一种。
优选的，所述可溶性钴盐为硝酸钴，所述可溶性金属盐为硝酸金属盐；
进一步优选的，所述可溶性钴盐为六水硝酸钴；所述可溶性金属盐为四水硝酸锰Mn(NO3)2·4H2O、六水硝酸铈Ce(NO3)3·6H2O和九水硝酸铁Fe(NO3)3·9H2O中的至少一种。
所述分散液中可溶性钴盐的浓度为0.1-0.4mol/L，可溶性金属盐的总浓度为0.01-0.05mol/L，碱的浓度为0.4-2.0mol/L；
所述搅拌的时间为1-6小时；所述清洗是指分别用超纯水和无水乙醇清洗；干燥的温度为40-100℃，时间为0.5-2h；
所述煅烧的温度为270-400℃，时间为0.5-4h。
优选的，所述炭黑与可溶性钴盐的摩尔比为(0.5-2):1。
上述的基于阳离子掺杂的钴氧化物催化剂在甲醛催化氧化中的应用。
优选的，甲醛催化氧化的条件为：甲醛初始浓度，小于150ppm；温度，40～150℃；气体体积空速为40～50L gcat -1h-1。
本发明的原理为：对于甲醛催化氧化催化剂，催化剂对氧分子的活化能力与提供的活性位点数量是影响催化性能的关键。目前的非贵金属催化剂往往因活化氧分子能力较弱或活性位点数量不足而难以实现甲醛的低温催化氧化。本发明所提供的催化剂在设计思路上引入异质离子掺杂来调节氧活性物种数量和活性位点数量以提高非贵金属催化剂的催化性能，并提供了简单易行的制备方法加以实现。本发明采用沉淀结合热处理两步合成了具有阳离子掺杂的钴氧化物催化剂。首先通过沉淀法得到阳离子掺杂的羟基钴氧化物前驱体；随后，通过调控热处理条件来得到富含氧缺陷数量的催化剂。在本发明的催化剂中，离子掺杂通过替换金属阳离子造成晶格膨胀可提高催化剂的氧缺陷含量。高度弥散的钴氧化物结合丰富的氧空位为甲醛催化氧化提供了大量的活性位点与吸附位点，提高了甲醛催化氧化的活性。综上，本发明所提供的甲醛催化氧化催化剂兼具高本征活性和丰富的活性位点。
进一步的，本发明在引入异质离子掺杂的基础上，还掺杂了碳形成复合相来调节氧活性物种数量和活性位点数量以提高非贵金属催化剂的催化性能，碳的引入使钴氧化物纳米片弥散分布可进一步增加活性位点数量。
相对于现有技术，本发明具有如下优点及有益效果：
(1)本发明提供的阳离子掺杂的钴氧化物催化剂材料有效的兼具优化本征活性和活性位数量。通过离子掺杂有效引入大量的氧空位，有效提高催化剂活性和稳定性；在100℃下实现甲醛完全氧化去除。
(2)本发明所得基于阳离子掺杂结合碳复合改性的钴基氧化物催化剂可在90℃下实现甲醛完全氧化去除且其具有较高的比质量反应速率(高达4.7μmol g-1min-1)；此外，其表现出优异的稳定性和耐湿性，其活性优于目前报道的大多数钴基氧化物催化剂。
(3)本发明的制备方法原料易得、工艺简单、便于量产。
附图说明
图1为本发明实施例1中所得Mn掺杂钴氧化物复合碳催化剂(记为：Co2.7Mn0.3O4/C)和参比样品的X射线衍射图。
图2为本发明实施例1中所得Mn掺杂钴氧化物复合碳催化剂(记为：Co2.7Mn0.3O4/C)和商用Co3O4和Mn3O4的拉曼光谱图。
图3为本发明实施例1中所得催化剂Co2.7Mn0.3O4/C的扫描电镜形貌图(a)；透射电镜形貌图(b)；选区电子衍射图谱(c)和高分辨电子显微照片(d)。
图4a为本发明实施例1中所得催化剂Co2.7Mn0.3O4/C在O1s区域的的X射线光电子能谱图。
图4b为本发明实施例1中所得催化剂Co2.7Mn0.3O4/C在Co 2p区域的的X射线光电子能谱图。
图4c为本发明实施例1中所得催化剂Co2.7Mn0.3O4/C在Mn 2p区域的的X射线光电子能谱图。
图5a为本发明实施例1中所得催化剂的甲醛催化氧化转化率性能随温度变化图。
图5b为本发明实施例1中所得催化剂的甲醛催化氧化质量比反应速率性能随温度变化图。
图6a为本发明实施例1中所得催化剂Co2.7Mn0.3O4/C的稳定性测试结果图。
图6b为本发明实施例1中所得催化剂Co2.7Mn0.3O4/C的耐湿性测试结果图。
图7为本发明实施例1和2中所得Mn、Ce、Fe掺杂钴氧化物复合碳催化剂(分别记为：Co2.7Mn0.3O4/C，Co2.7Ce0.3O4/C和Co2.7Fe0.3O4/C)的X射线衍射图。
图8为本发明实施例1和2中所得催化剂Co2.7Mn0.3O4/C，Co2.7Ce0.3O4/C和Co2.7Fe0.3O4/C的甲醛催化氧化性能图。
图9为本发明实施例1和3中所得不同钴锰比催化剂的X射线衍射图。
图10为本发明实施例1和3中所得不同钴锰比催化剂的甲醛催化氧化性能图。
图11为本发明实施例1和4中所得不同热处理温度催化剂的X射线衍射图。
图12为本发明实施例1和4中所得不同热处理温度催化剂的甲醛催化氧化性能图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式和保护范围不限于此。
实施例1
(1)催化剂制备：
Co2.7Mn0.3O4/C催化剂的合成：将10mmol Co(NO3)2·6H2O、1mmol Mn(NO3)2·4H2O、10mmol C(炭黑)和50mmol NaOH分散于50mL超纯水中，先后经磁力搅拌两小时、所得沉淀物经充分清洗(分别用超纯水、无水乙醇清洗)、真空干燥(60℃，2h)后空气气氛下煅烧(300℃,2h)制得目标催化剂Co2.7Mn0.3O4/C。
Co2.7Mn0.3O4的制备：采用沉淀结合热处理的方法制得。与样品Co2.7Mn0.3O4/C的制备方法类似，区别在于不加入炭黑，其它相同最后得到Co2.7Mn0.3O4。
参比样品Co3O4/C的制备：采用沉淀结合热处理的方法制得。与样品Co2.7Mn0.3O4/C的制备方法类似，区别在于不加入Mn(NO3)2·4H2O，其它相同最后得到参比样品Co3O4/C。
参比样品Mn3O4/C的制备：采用沉淀结合热处理的方法制得。与样品Co2.7Mn0.3O4/C的制备方法类似，区别在于不加入Co(NO3)2·6H2O，Mn(NO3)2·4H2O和C摩尔比由1：10改为1：1。其余条件与目标催化剂Co2.7Mn0.3O4/C一致，制得参比样品Mn3O4/C。
(2)催化剂的物相/结构/元素化学态表征：
本实施例所得催化剂Co2.7Mn0.3O4/C的X射线衍射、拉曼光谱和选区电子衍射图分别如图1、图2和图3(c)所示。结合XRD、拉曼光谱和选区电子衍射分析证明，锰元素掺杂进入四氧化三钴的晶格。扫描电镜和透射电镜观察(图3(a)、图3(b)和图3(d))发现，四氧化三钴以纳米片形式弥散分布于非晶碳表面，其片层厚度约1-5nm。
根据X射线光电子能谱分析(图4a和图4b)，所得催化剂Co2.7Mn0.3O4/C的O1s谱表明该催化剂表面存在大量的氧空位；此外，Co 2p与Mn 2p谱分别存在相应低价态的Co2+和Mn2+信号，进一步确证了催化剂表面存在氧空位。
(3)本实施例所得催化剂Co2.7Mn0.3O4/C催化性能测试：
不同温度下催化剂的催化活性变化(图5a)表明，Co2.7Mn0.3O4/C催化剂具有优异的催化反应活性，在90℃下即可将90ppm的甲醛完全催化氧化为CO2和H2O；Co2.7Mn0.3O4在100℃下即可将90ppm的甲醛完全催化氧化为CO2和H2O。同时与Co2.7Mn0.3O4催化剂相比(图5b)，具有更高的质量比反应速率(90℃时质量比反应速率高达4.7μmol m-2min-1)，说明其具有优异的低温催化活性，优于目前报道的大多数钴基非贵金属催化甲醛氧化催化剂。甲醛催化氧化反应条件：原料为90ppm甲醛与高纯空气混合气，气体体积空速为40L gcat -1h-1。
图6a和图6b给出了Co2.7Mn0.3O4/C催化剂的稳定性与耐湿型测试结果，从图6a可以看出，在24小时等温测试(温度90℃，湿度50％)下Co2.7Mn0.3O4/C催化剂的甲醛转化率仅出现轻微波动(83％±2％)；从图6b可以看出，在不同湿度条件下(温度90℃，湿度20％～70％)的甲醛转化率为80±3％，催化剂活性未出现明显衰减，说明该催化剂具备优异的稳定性与耐湿型。甲醛催化氧化反应条件：原料为90ppm甲醛与高纯空气混合气，气体体积空速为50L gcat -1h-1。
实施例2
(1)催化剂制备：
本实施例的合成方法中，仅将Mn(NO3)2·4H2O分别更换为Ce(NO3)3·6H2O和Fe(NO3)3·9H2O，其余制备条件与实施例1一致。
(2)催化剂的物相/结构表征：
本实施例所得催化剂CoxM3-xO4/C的X射线衍射如图7所示。根据XRD分析，制得的催化剂并无锰氧化物相生成，意味着在制备过程中锰离子可能进入了四氧化三钴的晶格。
(3)本实施例所得目标催化剂CoxM3-xO4/C催化性能测试：
不同温度下催化剂的催化性能变化(见图8)表明，不同阳离子掺杂对甲醛催化氧化活性影响较大。各种阳离子掺杂甲醛催化氧化性能由高到低顺序为Mn>Ce>Fe。其中Co2.7Mn0.3O4/C催化剂具有最优的催化反应活性，在90℃时即可将90ppm的甲醛完全催化氧化为CO2和H2O，表明该催化剂具有较好的低温催化活性；此外，其表现出较高的催化反应速率(4.7μmol m-2min-1)其活性优于多数目前报道的钴基非贵金属催化剂。甲醛催化氧化反应条件：原料为90ppm甲醛与高纯空气混合气，气体体积空速为40L gcat -1h-1。
实施例3
(1)催化剂制备：
本实施例的合成方法中，仅将钴锰投料比改为3：1、5：1、20：1和30：1，其余制备条件与实施例1一致。所得催化剂记为CoxMn3-xO4/C。
(2)催化剂的物相/结构表征：
本实施例所得催化剂CoxMn3-xO4/C的X射线衍射如图9所示。根据XRD分析，不同钴锰投料比样品的衍射峰均与Co3O4匹配良好。其中制得的催化剂CoxMn3-xO4/C随锰含量的增加，属于Co3O4的衍射峰强度减弱且向低角度偏移，说明锰离子掺杂进入四氧化三钴晶格。
(3)本实施例所得催化剂CoxMn3-xO4/C催化性能测试：
不同温度下催化剂的催化性能变化(图10)表明，CoxMn3-xO4/C催化剂催化氧化甲醛的活性与钴锰比有关，当钴锰比为10：1时最佳，而过低或过高的钴锰比皆不利于提高甲醛催化的活性。其中Co2.7Mn0.3O4/C催化剂在90℃时即可将90ppm的甲醛完全催化氧化为CO2和H2O，表明该催化剂具有较好的低温催化活性；其活性优于多数目前报道的钴基非贵金属催化剂。甲醛催化氧化反应条件：原料为90ppm甲醛与高纯空气混合气，气体体积空速为40Lgcat -1h-1。
实施例4
(1)催化剂制备：
本实施例的合成方法中，仅将热处理温度改为270℃、330℃、350℃和400℃，其余制备条件与实施例1一致。所得催化剂记为Co2.7M0.3O4/C-R，其中R为热处理温度。
(2)催化剂的物相/结构表征：
本实施例所得催化剂的X射线衍射如图11所示。根据XRD分析，不同热处理温度样品的衍射峰均与Co3O4匹配良好。同时随煅烧温度的升高，样品结晶度更好，晶粒更加粗大。
(3)本实施例所得催化剂催化性能测试：
不同温度下催化剂的催化性能变化(图12)表明，甲醛催化氧化的活性与前躯体煅烧温度有关。当热处理温度为300℃时最佳，而过低或过高的煅烧温度皆不利于提高甲醛催化的活性。其中Co2.7M0.3O4/C-300催化剂较参比样品表现出优异的甲醛催化活性，在90℃时即可将90ppm的甲醛完全催化氧化为CO2和H2O，表明该催化剂具有较好的低温催化活性；其活性优于多数目前报道的钴基非贵金属催化剂。甲醛催化氧化反应条件：原料为90ppm甲醛与高纯空气混合气，气体体积空速为40L gcat -1h-1。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (3)
1.一种基于阳离子掺杂的钴氧化物催化剂在甲醛催化氧化中的应用，其特征在于，甲醛催化氧化的条件为：甲醛初始浓度90~150ppm且不包括150ppm端点值；温度，80~150℃；气体体积空速为40~50 L gcat -1 h-1；
所述基于阳离子掺杂的钴氧化物催化剂中的阳离子进入钴氧化物晶格提高了氧缺陷含量；所述阳离子为Mn；
所述基于阳离子掺杂的钴氧化物催化剂还加入碳形成复合相，钴氧化物以纳米片形态分布于碳表面；化学式为CoxM3-xO4/C，其中2.25≤x≤2.85，M为Mn；制备方法包括如下步骤：
将可溶性钴盐、可溶性金属盐、炭黑、碱分散于去离子水中得分散液，搅拌后所得沉淀物经清洗、干燥、空气气氛下煅烧后制得基于阳离子掺杂的钴氧化物催化剂；所述可溶性金属盐中的金属为Mn，所述碱为氢氧化钠、氢氧化钾中的至少一种；所述搅拌的时间为1-6小时；所述煅烧的温度为270-330 ℃，时间为0.5-4 h；所述炭黑与可溶性钴盐的摩尔比为（0.5-2）:1。
2.根据权利要求1所述的应用，其特征在于，所述钴氧化物的纳米片为二十到一百纳米的横向尺寸和一到五纳米的厚度。
3.根据权利要求1所述的应用，其特征在于，所述可溶性钴盐为硝酸钴，所述可溶性金属盐为硝酸金属盐；
所述分散液中可溶性钴盐的浓度为0.1-0.4 mol/L，可溶性金属盐的总浓度为0.01-0.05mol/L，碱的浓度为0.4-2.0 mol/L；
所述清洗是指分别用超纯水和无水乙醇清洗；干燥的温度为40-100℃，时间为0.5-2h。
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