CN112246263B - 一种非金属表面等离子体催化剂及其制备方法和应用 - Google Patents
一种非金属表面等离子体催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于光催化水制氢领域和光催化环保领域，公开了一种非金属表面等离子体催化剂及其制备方法和应用，包括如下步骤：将Cd0.5Zn0.5S和Ti3C2分散在水中，然后，在保护气氛下进行水热反应，反应结束后洗涤，得到Ti3C2/Cd0.5Zn0.5S，干燥，获得非金属表面等离子体催化剂。本发明催化剂应用于光催化水(包括海水)产氢、降解水中有机物、去除挥发性有机物和恶臭有机物，具有光响应范围广，可有效分离光生电子和空穴对，光催化活性高。
Description
技术领域
本发明涉及光催化水制氢领域和光催化环保领域，具体地涉及一种具有非金属表面等离子体Ti3C2(MXene)组装特殊结构的Ti3C2(MXene)/Cd0.5Zn0.5S催化剂及其在光催化水(包括海水)制氢，光催化降解水中有机物,去除挥发性有机物和恶臭有机物中的应用。
背景技术
环境和可再生资源利用是人类生存在地球上的挑战，不断增加的温室气体排放和清洁能源成为全球经济和气候尚未解决的问题。为了人类可持续发展的需要，应综合利用资源，保护环境，与自然和谐相处；化石能源短缺和全球环境问题需要迫切解决。氢能，作为一种清洁无污染的能源，已经受到越来越多人的关注。氢气具有以下特点：导热好、易回收、燃烧性能好、损耗小，对环境友好，产物水无腐蚀性，单位质量的能量很高。当前制约氢能发展的主要因素之一在于氢气费用高。目前主要的氢气生产方法包括传统能源制氢(煤制氢、天然气制氢)，可再生能源制氢，水电解制氢及工业副产氢。煤气化制氢，经济成本/CNY·(kgH2)：8.3～19.5CNY/kgH2；能耗：190～325MJ/kg H2；温室气体释放：5000～11300g CO2/kgH2。天然气制氢，经济成本/CNY·(kgH2)：10.4～27.6CNY/kgH2；能耗：165～360MJ/kg H2；温室气体释放：8400g CO2/kgH2。热化学制氢，经济成本/CNY·(kgH2)：12.8～36.9CNY/kgH2；能耗：360～410MJ/kg H2；温室气体释放：360g～860g CO2/kgH2。可再生能源发电制氢，(风电制氢)经济成本/CNY·(kgH2)：22.3～59.8CNY/kgH2；能耗：9～12MJ/kg H2；温室气体释放：785g CO2/kg H2。(太阳能光伏发电制氢)经济成本/CNY·(kgH2)：36.6～61.3CNY/kgH2；能耗：30～80MJ/kgH2；温室气体释放：4600g CO2/kgH2。生物质气化制氢，经济成本/CNY·(kgH2)：9.7～22.2CNY/kgH2；能耗：4～20MJ/kg H2；温室气体释放：3000g CO2/kgH2。传统的制氢方法碳氢化合物蒸汽重整，电解水和重油氧化生成氢气,能耗和转化过程中的有害物质产生限制了友好氢能资源的开发。因此，通过太阳能将水转化为氢气被认为是有希望的解决这些问题的方法。光催化水制氢过程的由于光生电子和空穴的复合，使得制氢产量不高；光催化剂对太阳光谱吸收响应窄，太阳能利用不足。设计光催化剂应具有广泛的光响应范围，并且可以有效抑制光生电子-空穴的复合。另一方面，地球上的水资源97％是被海水覆盖，如果能够使得光催化水制备氢气的应用范围扩大到海水领域将会有十分重要的意义。于此同时，基于太阳能光催化生成电子-空穴对的原理，其在水中有机物降解，去除挥发性有机物和恶臭有机物也有明显的效果。
发明内容
针对现有技术的不足，本发明提出了一种非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂的制备及其应用，本发明采用组装非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂，由于非金属表面等离子体Ti3C2(MXene)扩展了对太阳光的吸收响应，有效地使光生电子-空穴分离，可以强化光催化制氢反应。
为了实现上述目的，本发明采用的技术方案如下：
一种非金属表面等离子体催化剂的制备方法，包括如下步骤：
将Cd0.5Zn0.5S和Ti3C2分散在水中，然后，在保护气氛下进行水热反应，反应结束后洗涤，得到Ti3C2/Cd0.5Zn0.5S，干燥，获得非金属表面等离子体催化剂。
优选地，所述Ti3C2在催化剂中的含量为1～7wt％。
优选地，所述Ti3C2在催化剂中的含量为5±1wt％。
优选地，所述水热反应的条件为：150～200℃反应12～24小时。
优选地，所述Ti3C2的制备：取Ti3AlC2，加入氢氟酸，其质量比为1：10-200，反应3～4天，使得Ti3AlC2中的铝溶出；然后过滤分离，洗涤至中性即可。
优选地，所述Cd0.5Zn0.5S的制备：取等摩尔的醋酸锌和醋酸镉，于水中搅拌30～60分钟，加入硫代乙酰胺和乙二胺，随后加入足量的水，进行水热反应，反应条件为180～220℃反应12～24小时，然后用去离子水洗涤，得到Cd0.5Zn0.5S。
上述方法制得的非金属表面等离子体催化剂在光催化水制氢，或者光催化降解水中有机物、去除挥发性有机物和恶臭有机物中的应用。
优选地，所述光催化水制氢是将催化剂分散于水中，光照至少30min；所述水为淡水或海水。
优选地，所述光催化水制氢用Na2SO4和Na2S作为牺牲剂，光照波长≥420nm。
与现有技术相比，本发明具有如下有益效果：
1.与光催化剂Cd0.5Zn0.5S相比，具有非金属表面等离子体作用，有效分离光生电子-空穴，极大地提高了光催化活性。
2.Ti3C2(MXene)/Cd0.5Zn0.5S耦合可以使得激发电子所需能量减小，光响应扩展到可见光区和红外光区，则本发明提出非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S应用于光催化水制氢反应，尤其是在红外区也有较好的活性。
3.非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂，形成的肖特基势垒相互协同作用有利于增强光催化活性。
4.非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂，应用于光催化水(包括海水)产氢,降解水中有机物,去除挥发性有机物和恶臭有机物；非金属表面等离子体Ti3C2(MXene)具有较好的导电性，可以和半导体Cd0.5Zn0.5S表面形成肖特基势垒，在半导体上产生的电子经肖特恩界面到达非金属表面等离子体Ti3C2(MXene)，所以电子在非金属表面等离子体Ti3C2(MXene)上富集，空穴在半导体上富集，抑制电子和空穴的复合。促进光催化水(包括海水)制氢反应，降解水中的有机物,去除挥发性有机物和恶臭有机物。
附图说明
图1是实施例1-3Cd0.5Zn0.5S，JCPDS NO.01-089-2943、Ti3C2/Cd0.5Zn0.5S的XRD图谱。
图2是5wt％Ti3C2/Cd0.5Zn0.5S光催化稳定性。
图3是Ti3C2，Cd0.5Zn0.5S，5wt％Ti3C2/Cd0.5Zn0.5S的HRTEM图谱。
图4是不同比例Ti3C2-Cd0.5Zn0.5S分别在海水和淡水中产氢的效果图。
图5是不同比例Ti3C2-Cd0.5Zn0.5S的光电流谱图。
图6是不同比例Ti3C2-Cd0.5Zn0.5S的阻抗谱图。
图7是不同比例Ti3C2-Cd0.5Zn0.5S的静态-荧光图。
图8是5wt％Ti3C2/Cd0.5Zn0.5S与已经报道的光催化剂应用于海水中产氢的效果图。
图9是非金属表面等离子体效应的谱图。
图10是Ti3C2和Cd0.5Zn0.5S物理混合、单独Cd0.5Zn0.5S在淡水中产氢的效果图。
图11是5％Ti3C2/Cd0.5Zn0.5S和Cd0.5Zn0.5S的UV漫反射图。
图12是5％Ti3C2/Cd0.5Zn0.5S和Cd0.5Zn0.5S的拉曼图谱。
具体实施方式
以下结合附图和具体实施例对本发明作具体的介绍，但不限定本发明的保护范围。
实施例1：制备Cd0.5Zn0.5S粉体
取等摩尔的醋酸锌和醋酸镉，于去离子水中搅拌60分钟，加入硫代乙酰胺和乙二胺，随后加入足够的去离子水，转入高压釜中水热反应，在180℃条件下，反应12小时，在常温下，用去离子水洗涤，然后冻干，得到Cd0.5Zn0.5S粉粒。
实施例2：制备Ti3C2粉体
取1.0g Ti3AlC2，加入氢氟酸150毫升，反应4天，使得Ti3AlC2中的铝溶出。然后过滤分离，用去离子水洗涤分离，使洗涤液成为中性。冻干2天，得到Ti3C2粉末。
实施例3：制备非金属表面等离子体Ti3C2(MXene)/Cd0.5Zn0.5S光催化剂
将0.05g的Cd0.5Zn0.5S溶于40mL脱氧去离子水中，然后，加入适量的Ti3C2水溶液中，在氩气条件保护下搅拌2小时；然后，在水热条件下，200℃反应24小时，在常温下，用去离子水洗涤，得到Ti3C2(MXene)/Cd0.5Zn0.5S粉体，真空干燥24小时，获得用于光催化的催化剂。调控Ti3C2的比例获得Ti3C2含量分别为1wt％、3wt％、5wt％和7wt％的Ti3C2/Cd0.5Zn0.5S光催化剂。
图5的光电流谱图，当有Ti3C2和Cd0.5Zn0.5S合成新材料时，可以明显提升其光生电流密度，大量的电子产生利于光催化的效果。
图6的阻抗谱图，阻抗值大小主要由电子-空穴的交换电阻以及自身的电子或空穴迁移电阻决定的。当有ti3C2和Cd0.5Zn0.5S合成新材料时，可以明显改善电子-空穴的反应能力，同时提高电子或空穴在材料内的迁移能力，从而有利于光催化的效果。
图7的静态-荧光图，荧光激发强度可以评价材料内部电子-空穴重新聚合的能力，当Ti3C2和Cd0.5Zn0.5S合成新材料时，明显的降低了电子-空穴重新聚合的趋势，从而有利于光催化的效果。图7和图5，图6的实验结果都是相符合的，进一步的验证了Ti3C2和Cd0.5ZN0.5S合成的新材料在光催化方面的高效性。
图9中的实心圆是Ti3C2，当有光辐射时通过有限元的计算模拟Ti3C2周围的等离子体电场。加深的区域都是表示有很强的电场。这张图从理论计算模拟的方面证明非金属性的Ti3C2也具有表面等离子体效应。
图11是UV漫反射图以证明合成的5％Ti3C2/Cd0.5Zn0.5S和Cd0.5zn0.5S比较而言，从大约510纳米的波长开始5％Ti3C2/Cd0.5Zn0.5S仍然有着光谱吸收能力。5％Ti3C2/Cd0.5Zn0.5S图谱上扬的轨迹相对Cd0.5Zn0.5S图谱下垂的轨迹展示着明显的表面等离子体现象。图12是这两者的拉曼图谱的对比，因为表面等离子有着拉曼增强的效果，所以新合成的5％Ti3C2/Cd0.5Zn0.5S相对于Cd0.5Zn0.5S有着较强的拉曼现象。
实施例4：不同百分比的Ti3C2(MXene)/Cd0.5Zn0.5S光催化水制氢
取50毫克1～7wt％Ti3C2/Cd0.5Zn0.5S粉体分散于70毫升去离子水中，用0.25MNa2SO4和0.35M Na2S作为牺牲剂，在氮气条件下，光源为300W氙灯光照1h，每小时取样在线气相色谱仪(GC7900,TCD检测器；
分子筛，氮气作为载气)检测产氢情况，效果详见图4，其中5wt％的Ti3C2/Cd0.5Zn0.5S的产氢效率达到14mmol/g/h。
实施例5：Ti3C2(MXene)/Cd0.5Zn0.5S光催化海水制氢
取50毫克1～7wt％Ti3C2/Cd0.5Zn0.5S粉体分散于70毫升海水中，用0.25MNa2SO4和0.35M Na2S作为牺牲剂，在氮气条件下，光源为300W氙灯光照1h，每小时取样在线气相色谱仪(GC7900,TCD检测器；
分子筛，氮气作为载气)检测产氢情况，效果详见图4，其中5wt％的Ti3C2/Cd0.5Zn0.5S的产氢效率达到9mmol/g/h。
从图8可见，本发明5wt％Ti3C2/Cd0.5Zn0.5S催化剂的产氢量远高于现有催化剂。
Ti3C2和Cd0.5Zn0.5S的物理混合后的光催化效果详见图10，说明了简单的加成混合并不能达到增强性的光催化效果。Ti3C2-Cd0.5Zn0.5S只有经过本发明方法制备才能达到比较好的光催化效果。
实施例6：Ti3C2(MXene)/Cd0.5Zn0.5S光催化降解水中有机物
取50毫克5wt％Ti3C2/Cd0.5Zn0.5S粉体于70毫升分别含有10mg/L浓度的环丙沙星，甲基橙，双酚A溶液中，以光源为300W Xenon lamp光照，每2分钟取样以高效液相色谱检测配置溶液中有机物的浓度以确定光催化降解的效果。所有被测有机物的降解效率在较短时间(2min)内都超过90％以上，其中降解效率：环丙沙星为93.23％，甲基橙为94.87％，双酚A为96.75％。
实施例7：Ti3C2(MXene)/Cd0.5Zn0.5S光催化去除挥发性有机物和恶臭有机物
取50毫克5wt％Ti3C2(MXene)/Cd0.5Zn0.5S粉体置于密闭容器中分别通入氯代烃,甲苯，甲醛气体使得已经抽真空预处理的密闭容器内挥发有机物和恶臭有机物的浓度控制在200ppb，以光源为300W Xenon lamp光照，以气相色谱在线自动取样检测容器内中有机物的浓度以确定光催化去除挥发性有机物和恶臭有机物的效果。所有被测有机物的去除效率在较短时间(10min)内都超过80％以上(氯代烃83.98％，甲苯89.15％，甲醛86.49％)。
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，其他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 (9)
1.一种应用于光催化淡水和海水制氢、光催化降解水中有机物、去除挥发性有机物和恶臭有机物的非金属表面等离子体催化剂的制备方法，其特征在于，包括如下步骤：
将Cd0.5Zn0.5S和Ti3C2分散在水中，然后，在保护气氛下进行水热反应，反应结束后洗涤，得到Ti3C2/Cd0.5Zn0.5S，干燥，获得非金属表面等离子体催化剂；所述Ti3C2在非金属表面等离子体催化剂中的含量为5～7wt%。
2.根据权利要求1所述的制备方法，其特征在于，所述Ti3C2在非金属表面等离子体催化剂中的含量为5wt%。
3.根据权利要求1或2所述的制备方法，其特征在于，所述水热反应的条件为：150～200℃ 反应12～24小时。
4.根据权利要求1或2所述的制备方法，其特征在于，所述Ti3C2的制备：取Ti3AlC2，加入氢氟酸，其质量比为1：10-200，反应3～4天，使得Ti3AlC2中的铝溶出；然后过滤分离，洗涤至中性即可。
5.根据权利要求1或2所述的制备方法，其特征在于，所述Cd0.5Zn0.5S的制备：取等摩尔的醋酸锌和醋酸镉，于水中搅拌30～60分钟，加入硫代乙酰胺和乙二胺，随后加入足量的水，进行水热反应，反应条件为180～220℃ 反应12～24小时，然后用去离子水洗涤，得到Cd0.5Zn0.5S。
6.权利要求1~5任意一项所述方法制得的非金属表面等离子体催化剂。
7.权利要求6所述非金属表面等离子体催化剂在光催化水制氢，或者光催化降解水中有机物、去除挥发性有机物和恶臭有机物中的应用。
8.根据权利要求7所述的应用，其特征在于，所述光催化水制氢是将催化剂分散于水中，光照至少30min；所述水为淡水或海水。
9.根据权利要求8所述的应用，其特征在于，所述光催化水制氢用Na2SO4和Na2S作为牺牲剂，光照波长≥420nm。
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