CN112121854B - 自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂及其制备方法和应用 - Google Patents
自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了自组装四(4‑羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂及其制备方法和应用,所述光催化剂由自组装四(4‑羧基苯基)卟啉(SA‑TCPP)和氧掺杂氮化碳纳米片(O‑CN)通过静电作用和π‑π相互作用复合而成,其中O‑CN和SA‑TCPP的质量比范围为1:0.001~0.8;所述SA‑TCPP通过原位法修饰到O‑CN上。与现有技术相比,本发明具有以下优点:(1)本发明所述的光催化剂相比于现有技术中的O‑CN及SA‑TCPP拥有更为优异的光催化降解污染物和光解水产氧的性能;(2)本发明所述方法绿色安全、工艺简单,成本低廉,适合于工业化大批量生产,具有较高的应用前景和实用价值。
Description
技术领域
本发明属于光催化材料技术领域,涉及一种异质结光催化剂,具体为自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂及其制备方法和应用。
背景技术
氮化碳是一种非金属n型有机半导体可见光光催化剂,具有合成方便、成本低、稳定性好、无生物毒性、结构易调控等优点,因而广泛应用于降解污染物和光解水等方面。但是,传统缩聚法制备的氮化碳颗粒尺寸大、比表面积低、可见光利用率低、光生电子-空穴对复合几率高,致使其光催化活性不够理想。因此,开发出具有纳米结构形貌,宽可见光谱响应范围以及快速的光生载流子分离和迁移能力的氮化碳基光催化剂意义重大。
自组装四(4-羧基苯基)卟啉(SA-TCPP)是一种新型n型有机超分子半导体光催化剂,具有独特电子结构和良好的光电特性。通过超分子自组装技术可以把单分子四(4-羧基苯基)卟啉(TCPP)从无序状态聚集成纳米尺寸的超分子单元,利用分子间弱相互作用的加合和协同实现分子聚集体中的电子转移和能量传递,使其拥有更好的光学特性,表现出优异的光催化效率,因而广泛应用于降解污染物、光解水产氧和抗肿瘤等方面。但是,SA-TCPP的光生电子-空穴对的复合几率高、且光还原能力较弱,影响其在光催化领域的应用前景。
发明内容
解决的技术问题:为了克服现有技术的不足,获得一种具有纳米结构形貌,宽可见光谱响应范围以及快速的光生载流子分离和迁移能力的光催化剂,本发明提供了自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂及其制备方法和应用。
技术方案:自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,所述光催化剂由自组装四(4-羧基苯基)卟啉和氧掺杂氮化碳纳米片通过静电作用和π-π相互作用复合而成,其中氧掺杂氮化碳纳米片和自组装四(4-羧基苯基)卟啉的质量比范围为1:0.001~0.8;所述自组装四(4-羧基苯基)卟啉通过原位法修饰到氧掺杂氮化碳纳米片上。
自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂的制备方法,所述方法以3-氨基-1,2,4-三氮唑为原料,通过热刻蚀-水热相结合的方法制备氧掺杂氮化碳纳米片,通过自组装法制备四(4-羧基苯基)卟啉超分子,最后通过原位法将自组装四(4-羧基苯基)卟啉修饰到氧掺杂氮化碳纳米片上。
优选的,所述方法具体步骤为:
(1)以3-氨基-1,2,4-三氮唑为原料,在空气气氛下进行煅烧,制备得到块状氮化碳,再将块状氮化碳研磨后在空气气氛下进行二次煅烧,制备得到氮化碳纳米片,然后将氮化碳纳米片超声分散在过氧化氢水溶液中,并进行水热反应,反应完后冷却,进行固液分离收集沉淀,将沉淀干燥研磨成粉,制备得到氧掺杂氮化碳纳米片;
(2)将四(4-羧基苯基)卟啉分散于强碱溶液中进行加热搅拌,使得四(4-羧基苯基)卟啉完全溶解,形成四(4-羧基苯基)卟啉溶液;
(3)将步骤(1)中所得氧掺杂氮化碳纳米片超声分散在水中,加入步骤(2)中所得四(4-羧基苯基)卟啉溶液,进行搅拌超声混合,再加入强酸溶液进行加热搅拌,直至溶液pH变为中性,反应结束后进行固液分离收集沉淀,沉淀经洗涤干燥并研磨,即得自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂。
优选的,步骤(1)中所述煅烧包括依次进行的升温加热阶段和恒温阶段;所述升温加热阶段的升温速率为1~12℃/min;所述恒温阶段的温度为450~600℃,恒温时间为1~8h;所述超声功率为200~800W,超声频率为10~50kHz,超声时间为5~60min。
优选的,步骤(1)中所述过氧化氢水溶液的浓度为0.1~40vol%,氮化碳与过氧化氢水溶液的质量体积比g/mL为1:30~150;所述水热反应温度为80~150℃,反应时间为2~10h。
优选的,步骤(2)的反应体系中加入强碱溶液浓度为0.01~10mol/L,所述四(4-羧基苯基)卟啉与强碱溶液的质量体积比g/mL为1:10~200,所述的强碱为氢氧化钾或氢氧化钠;所述加热反应的温度为50~150℃,反应时间为0.1~10h。
优选的,步骤(3)中所述氧掺杂氮化碳纳米片与水的质量体积比mg/mL为1:0.1~10;所述超声功率为200~800W,超声频率为10~50kHz,超声处理时间为0.1~5h;所述氧掺杂氮化碳纳米片与自组装四(4-羧基苯基)卟啉的质量比为1:0.001~0.8,所述搅拌的反应时间为0.5~5h;反应体系中加入强酸溶液浓度为0.01~10mol/L,四(4-羧基苯基)卟啉与强酸的质量体积比g/mL为1:1~200,所述的强碱为盐酸、硫酸或硝酸;所述加热反应温度为30~150℃,搅拌的反应时间为0.1~10h。
所述的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂在制备污染物降解化合物中的应用。
所述的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂在制备光解水产氧化合物中的应用。
本发明所述自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂及其制备方法的原理在于:本发明采用原位法,一方面,以3-氨基-1,2,4-三氮唑为前驱体得到的块状氮化碳相较于以单氰胺/双氰胺/三聚氰胺/尿素/硫脲为前驱体煅烧制备的块状氮化碳,具有更窄的带隙和更宽的光谱响应;二次煅烧则可以将块状氮化碳进一步热刻蚀成氮化碳纳米片,改善其光生载流子的迁移能力;同时,水热处理可以在氮化碳纳米片结构中掺入氧元素,增强其光吸收,调节其能带结构,并且能够使O-CN表面带正电荷。另一方面,通过自组装法,使TCPP在碱性条件下溶解于水中,再加入酸性溶液使TCPP分子之间的π-π作用以及羧酸基团之间的氢键作用自组装形成表面带有负电荷超分子纳米颗粒。而在TCPP自组装的过程中加入O-CN,SA-TCPP和O-CN之间可以通过静电作用和π-π相互作用进行结合,原位形成SA-TCPP/O-CN异质结光催化剂。
本发明通过前驱体优化、形貌调控和元素掺杂三种手段来提升氮化碳进行光催化作用的空间和电子结构,SA-TCPP超分子纳米颗粒复合实现氮化碳在可见光区域光谱吸收范围的拓展以及光生电荷的快速转移,制备出具有优异的降解污染物和产氧性能的SA-TCPP/O-CN异质结光催化剂。
本发明采用原位法,在TCPP自组装的过程中与O-CN通过静电作用和π-π相互作用进行原位结合,制备了SA-TCPP/O-CN异质结光催化剂;在SA-TCPP/O-CN体系中,O-CN与SA-TCPP两者的能带位置交叉排列,有利于n-n型异质结的形成和内置电场的构建,进而促进了异质界面处光生电子-空穴对的分离和转移;同时,SA-TCPP和O-CN间的π-π相互作用可以引起电子离域效应,促进光生电子的迁移。与O-CN相比,SA-TCPP/O-CN异质结具有更宽的光响应范围、更快的光生电子-空穴对的分离效率以及更强的光氧化能力,对于提高光催化剂的应用前景和实用价值具有重要的意义;另外原位复合法具有高效、绿色、温和的特点。
有益效果:(1)本发明所述的光催化剂相比于现有技术中的O-CN及SA-TCPP拥有更为优异的光催化降解污染物和光解水产氧的性能;(2)本发明所述方法绿色安全、工艺简单,成本低廉,适合于工业化大批量生产,具有较高的应用前景和实用价值。
附图说明
图1为实施例1制备的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片与对比例1制备的氧掺杂氮化碳纳米片在可见光下对双酚A的降解性能对比图;其中,(a)双酚A浓度随时间的变化曲线对比图;(b)降解双酚A的表观速率常数(k)对比;
图中:实施例1制备的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片简称SA-TCPP/O-CN,以加入SA-TCPP量为标准命名,SA-TCPP与O-CN的质量比分别为10%、20%、30%、40%、50%、60%的样品分别记为SA-TCPP/O-CN-10%、SA-TCPP/O-CN-20%、SA-TCPP/O-CN-30%、SA-TCPP/O-CN-40%、SA-TCPP/O-CN-50%、SA-TCPP/O-CN-60%,对比例1制备的氧掺杂氮化碳纳米片简称O-CN;
图2为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的自组装四(4-羧基苯基)卟啉在可见光下对2,4-二氯酚的降解性能,对比例2制备的自组装四(4-羧基苯基)卟啉简称SA-TCPP;其中,(a)降解2,4-二氯酚的速率曲线对比图;(b)降解2,4-二氯酚的表观速率常数(k)对比;
图3为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP在可见光下产氧性能对比图;
图4为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP在水溶液中的Zeta电位图;
图5为实施例1中制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP的TEM对比图;其中,(a)O-CN、(b)SA-TCPP和(c)SA-TCPP/O-CN-40%的TEM图像;
图6为实施例1制备的SA-TCPP/O-CN与对比例1制备的O-CN、对比例2制备的SA-TCPP的XRD对比图;
图7为实施例1制备的SA-TCPP/O-CN与对比例1制备的O-CN、对比例2制备的SA-TCPP的FTIR对比图;
图8为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP的DRS对比图;
图9为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN的光电性能对比图;其中,(a)O-CN和SA-TCPP在光暗交替下的光电流响应图;(b)O-CN和SA-TCPP在黑暗和可见光下的电化学阻抗Nyquist图;
图10为实施例1制备的SA-TCPP/O-CN与对比例1制备的O-CN、、对比例2制备的SA-TCPP的PL对比图;
图11为对比例1制备的O-CN和对比例2制备的SA-TCPP的能带结构对比图,其中,(a)O-CN和SA-TCPP的能带计算;(b)O-CN和SA-TCPP的Mott-Schottky曲线。
具体实施方式
以下实施例进一步说明本发明的内容,但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下,对本发明方法、步骤或条件所作的修改和替换,均属于本发明的范围。若未特别指明,实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
下述实施例中,采用JEOL JEM-2100型透射电子显微镜,电子束加速电压为200kV,拍摄透射电镜(TEM)图像;采用Bruker D2-phaserX射线衍射仪(CuKα,30kV,10mA)研究样品的X射线衍射光谱(XRD);采用Nicolet iS10光谱仪获得样品的红外光谱(FTIR);采用Zetasizer nano ZS分析仪测定样品的Zeta电位;采用Hitachi F-7000荧光光谱仪在激发波长λ=370nm下测定样品的光致发光光谱(PL);采用Shimadzu UV-3600Plus紫外可见分光光度计记录样品的漫反射光谱(DRS)。
实施例1
一种自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,所述光催化剂的制备方法包括如下步骤:
首先,将3-氨基-1,2,4-三氮唑置于坩埚中,放入马弗炉内,以2℃/min的速率升温到550℃煅烧4h,将产物研磨得到块状氮化碳;将块状氮化碳研磨,置于坩埚中,放入马弗炉内,以5℃/min的速率升温到500℃进行二次煅烧2h,将产物研磨得到氮化碳纳米片;将0.9g氮化碳纳米片分散在100mL 30vol%H2O2水溶液中并超声(560W,40kHz)30min,再将分散液转移到水热釜中,在120℃下加热6h,离心收集沉淀,用水洗涤沉淀数次,干燥后研磨成粉,得到的粉末产物即为氧掺杂氮化碳纳米片(O-CN)。其次,将310mg TCPP溶解于11mL KOH(1mol/L)中,加热搅拌30min,使固体完全溶解,形成TCPP储备液。最后,称取100mg O-CN分散在30mL去离子水中并超声(560W,40kHz)2h,加入一定体积的TCPP储备液,其中TCPP相对于O-CN的质量分数分别为10%、20%、30%、40%、50%、60%,搅拌60min,超声(560W,40kHz)15min,然后在50℃的水浴中加热,并通过恒压滴液漏斗向溶液中滴加0.1mol/L盐酸溶液,直至pH变为中性,在50℃的水浴中加热搅拌1h,离心收集沉淀,用水洗涤沉淀数次,干燥后研磨成粉,所得产物即为自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片(SA-TCPP/O-CN)异质结光催化剂。
实施例2
一种自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,所述光催化剂的制备方法包括如下步骤:
首先,将3-氨基-1,2,4-三氮唑置于坩埚中,放入马弗炉内,以1℃/min的速率升温到450℃煅烧1h,将产物研磨得到块状氮化碳;将块状氮化碳研磨,置于坩埚中,放入马弗炉内,以1℃/min的速率升温到450℃进行二次煅烧1h,将产物研磨得到氮化碳纳米片;将1g氮化碳纳米片分散在30mL 0.1vol%H2O2水溶液中并超声(200W,10kHz)5min,再将分散液转移到水热釜中,在80℃下加热2h,离心收集沉淀,用水洗涤沉淀数次,干燥后研磨成粉,得到的粉末产物即为氧掺杂氮化碳纳米片(O-CN)。其次,将310mg TCPP溶解于3.1mL KOH(0.01mol/L)中,加热搅拌0.1h,使固体完全溶解,形成TCPP储备液。最后,称取100mg O-CN分散在10mL去离子水中并超声(200W,10kHz)0.1h,加入一定体积的SA-TCPP溶液,其中SA-TCPP相对于O-CN的质量分数分别为0.1%,搅拌0.5h,超声(200W,10kHz)0.1h,然后在30℃的水浴中加热,并通过恒压滴液漏斗向溶液中滴加0.01mol/L盐酸溶液,直至pH变为中性,在30℃的水浴中加热搅拌0.1h,离心收集沉淀,用水洗涤沉淀数次,干燥后研磨成粉,所得产物即为自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片(SA-TCPP/O-CN)异质结光催化剂。
实施例3
一种自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,所述光催化剂的制备方法包括如下步骤:
首先,将3-氨基-1,2,4-三氮唑置于坩埚中,放入马弗炉内,以12℃/min的速率升温到600℃煅烧8h,将产物研磨得到块状氮化碳;将块状氮化碳研磨,置于坩埚中,放入马弗炉内,以12℃/min的速率升温到600℃进行二次煅烧8h,将产物研磨得到氮化碳纳米片;将1g氮化碳纳米片分散在150mL 40vol%H2O2水溶液中并超声(800W,50kHz)60min,再将分散液转移到水热釜中,在150℃下加热10h,离心收集沉淀,用水洗涤沉淀数次,干燥后研磨成粉,得到的粉末产物即为氧掺杂氮化碳纳米片(O-CN)。其次,将310mg TCPP溶解于62mL KOH(10mol/L)中,加热搅拌10h,使固体完全溶解,形成TCPP储备液。最后,称取100mg O-CN分散在1000mL去离子水中并超声(800W,50kHz)5h,加入一定体积的SA-TCPP溶液,其中SA-TCPP相对于O-CN的质量分数分别为80%,搅拌5h,超声(800W,50kHz)5h,然后在150℃的水浴中加热,并通过恒压滴液漏斗向溶液中滴加10mol/L盐酸溶液,直至pH变为中性,在150℃的水浴中加热搅拌10h,离心收集沉淀,用水洗涤沉淀数次,干燥后研磨成粉,所得产物即为自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片(SA-TCPP/O-CN)异质结光催化剂。
对比例1
热刻蚀-水热法制备氧掺杂氮化碳纳米片:将3-氨基-1,2,4-三氮唑置于坩埚中,放入马弗炉内,以2℃/min的速率升温到550℃煅烧4h,将产物研磨得到块状氮化碳;将块状氮化碳研磨,置于坩埚中,放入马弗炉内,以5℃/min的速率升温到500℃进行二次煅烧2h,将产物研磨得到氮化碳纳米片;将0.9g氮化碳纳米片分散在100mL 30vol%H2O2水溶液中并超声(560W,40kHz)30min,再将分散液转移到水热釜中,在120℃下加热6h,离心收集沉淀,用水洗涤沉淀数次,干燥后研磨成粉,得到的粉末产物即为氧掺杂氮化碳纳米片(O-CN)。
对比例2
自组装法制备自组装四(4-羧基苯基)卟啉:将310mg TCPP溶解于11mL KOH(1mol/L)中,加热搅拌30min,使固体完全溶解,形成TCPP储备液。随后,将一定量的TCPP储备液置于50℃的水浴中加热,通过恒压滴液漏斗向溶液中滴加0.1mol/L HCl溶液,直至pH变为中性。待混合溶液冷却后,用超纯水洗涤,抽滤收集所获沉淀,最后进行真空干燥,得到的产物即为自组装四(4-羧基苯基)卟啉(SA-TCPP)。
针对实施例1-3和对比例1-2获得的产品进行测试,结果及分析如下:
1、光催化降解污染物性能测试
采用双酚A(BPA)和2,4-二氯酚(2,4-DCP)作为目标降解物,在可见光下考察SA-TCPP/O-CN异质结光催化剂的降解活性,可见光采用500W的氙灯为光源加420nm滤光片,平均光强为30mW/cm2;取10ppm的双酚A溶液或者5ppm的2,4-二氯酚溶液50mL,加入25.0mg的光催化剂,先将分散液超声分散15min,然后在黑暗环境中搅拌1h使得光催化剂和目标污染物间达到吸附平衡;打开氙灯光源开始光催化反应,每隔1h取2mL反应溶液,离心(转速为11000rpm/min)去除溶液中的光催化剂,用0.22μm水系滤膜过滤上清液;通过高效液相色谱(HPLC)检测上清液中BPA(280nm处)和2,4-DCP(284nm处)的浓度(Waters-C18,甲醇/水体积比为60:40,流速1mL/min)。
图1为实施例1制备的SA-TCPP/O-CN与对比例1制备的O-CN在可见光下对双酚A的降解性能对比图。由图1(a)可知,在可见光(λ>420nm)下,与O-CN相比,SA-TCPP/O-CN复合材料的光催化活性显著提升。随着SA-TCPP负载量的增加,复合材料的光催化活性呈现出先增强后减弱的趋势。其中当SA-TCPP负载量为40wt%时,复合材料的光催化活性最佳。通过拟合准一级动力学方程得到光催化降解的表观速率常数k(图1(b)),SA-TCPP/O-CN-40%的表观速率常数k为0.1501h-1,约是O-CN(0.0407h-1)的3.7倍,这一结果表明SA-TCPP与O-CN复合成异质结材料确实可以起到提高O-CN光催化降解活性的作用。证明相比于O-CN和SA-TCPP,自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂拥有更为优异的光催化降解污染物性能。
图2为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP在可见光下对2,4-二氯酚的降解性能。由图2(a)可知,在可见光(λ>420nm)下,与O-CN和SA-TCPP相比,SA-TCPP/O-CN-40%在可见光下对2,4-DCP的降解效果最佳。通过拟合准一级动力学方程(图2(b))计算得到三者的光催化降解表观速率常数k,SA-TCPP/O-CN-40%的速率常数k为0.0619h-1,约是O-CN(0.0353h-1)的1.8倍,约是SA-TCPP(0.0503h-1)的1.2倍,这一结果进一步表明自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂性能的提升是O-CN和SA-TCPP协同作用的结果。
2、光催化产氧性能测试
用Labsolar-IIIAG系统(PerfectLight)进行光催化产氧实验,光源为装有截止滤光片(λ>420nm)的300W氙灯;称取25mg样品粉末加入100mL AgNO3水溶液(10mmol/L)中,超声30min使其分散均匀;打开氙灯光源开始光催化反应,每隔0.5h使用气相色谱仪(GC7920,TCD检测器,载气为Ar)检测产生的氧气量。
图3为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP在可见光下产氧性能对比图。由图3可知,以AgNO3为电子受体,降解活性最佳的SA-TCPP/O-CN-40%异质结材料的产氧能力同样得到了明显提升,在可见光照射3小时的产氧量为196.11μmol g-1,约是O-CN(42μmol g-1)的4.7倍,约是SA-TCPP(73.92μmol g-1)的2.7倍,这一结果进一步表明自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂性能的提升是O-CN和SA-TCPP协同作用的结果。
图4为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP在水溶液中的Zeta电位图。由图4可知,O-CN和SA-TCPP的平均Zeta电位分别为12.93mV和-29.23mV。因此,O-CN与SA-TCPP能够在静电相互作用下结合。而SA-TCPP/O-CN-40%复合材料的平均Zeta电位为-12.63mV,与O-CN相比,表面电荷发生较大变化,证明本发明用原位法可以将自组装四(4-羧基苯基)卟啉与氧掺杂氮化碳纳米片通过静电作用成功复合。
图5为实施例1中SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP的TEM对比图。如图5(a)所示,O-CN为纳米片结构,尺寸约为几百纳米;SA-TCPP呈现出直径在5~20nm的纳米晶结构(图5(b));图5(c)为SA-TCPP/O-CN-40%的TEM图,可以看到SA-TCPP纳米颗粒沉积在O-CN表面上,证明本发明用原位法可以将自组装四(4-羧基苯基)卟啉与氧掺杂氮化碳纳米片成功复合。
图6为实施例1制备的SA-TCPP/O-CN与对比例1制备的O-CN、对比例2制备的SA-TCPP的XRD对比图。如图6所示,O-CN在13.3°和28.2°处出现的两个特征峰(100)峰和(002)峰,分别对应平面内重复的七嗪单元和共轭C-N杂环的层状结构堆积。SA-TCPP在15°~30°范围内的宽衍射峰表明了材料内部的π-π堆积结构和纳米晶的小尺寸。SA-TCPP/O-CN复合材料中,对应于O-CN的28.2°处的特征峰明显变宽,这说明SA-TCPP与O-CN之间存在相互作用力。随着SA-TCPP质量百分比的增加,复合材料中对应于SA-TCPP的18°处的特征峰逐渐增强,表明SA-TCPP与O-CN成功复合。证明本发明用原位法可以将自组装四(4-羧基苯基)卟啉与氧掺杂氮化碳纳米片通过π-π相互作用成功复合。
图7为实施例1制备的SA-TCPP/O-CN与对比例1制备的O-CN、对比例2制备的SA-TCPP的FTIR对比图。如图7所示,O-CN在3000cm-1~3600cm-1、1200cm-1~1800cm-1和813cm-1处存在特征吸收带,分别对应于N-H与O-H的伸缩振动、芳香杂环的伸缩振动和七嗪单元的简正振动。SA-TCPP在3200cm-1~3600cm-1范围内的宽峰分别对应于卟啉中间环中的N-H和羧基基团中的O-H的伸缩振动;600cm-1~1520cm-1的典型振动带,归因于吡咯环中的N-H、C-H、C=C和C=N的伸缩振动。此外,SA-TCPP位于1176cm-1和1702cm-1处的峰分别归因于C-O和C=O的伸缩振动,证明了SA-TCPP结构中羧基取代基的存在。随着SA-TCPP负载量的增加,复合材料中对应于SA-TCPP以3440cm-1为中心的峰愈发明显,证明本发明用原位法可以将自组装四(4-羧基苯基)卟啉与氧掺杂氮化碳纳米片成功复合。
图8为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN、对比例2制备的SA-TCPP的DRS对比图。如图8所示,O-CN在400nm和450-800nm处显示出两个吸收带,400nm处吸收带归属于共轭七嗪环中的π-π*跃迁,450-800nm的吸收带源于七嗪环中的n-π*跃迁;SA-TCPP表现出较宽的光吸收范围,几乎覆盖了整个可见光区;在与SA-TCPP复合后,SA-TCPP/O-CN-40%复合材料可见光区域的光吸收性能得到了显著提高,吸收边缘扩展至约750nm,从而能够在光照下产生更多的光生载流子,有利于光催化活性的提升。证明本发明用原位法制备的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂的光谱响应范围得到显著扩展。
3、光电性能测试
光电流测量在CHI 660D电化学工作站(Chenhua Instrument)上进行,标准三电极系统包括对电极即铂丝,参比电极即饱和甘汞电极和工作电极,同时将0.1mol/L Na2SO4溶液作为电解质。工作电极制备方法如下:将2mg样品粉末分散在1mL无水乙醇中,将悬浮液涂覆在氧化铟锡(ITO)玻璃表面,室温干燥并在180℃下加热5h。使用具有400nm截止滤光片的300W氙灯(CEL-HXF 300,中教金源)作为可见光源。光电流响应测试在0.0V下进行;交流阻抗谱(EIS)光谱在5mV的AC电压下并在0.05Hz至105Hz的范围内记录;莫特-肖特基(Mott-Schottky,MS)曲线测试的起始电压设为-0.5V-0.5V,步长为0.05V。
图9为实施例1制备的SA-TCPP/O-CN-40%与对比例1制备的O-CN的光电性能对比图。如图9(a)所示,电流强度在开灯后迅速增加并保持相对恒定,而在关灯时瞬时降低。在可见光下,SA-TCPP/O-CN-40%的光电流较O-CN相比得到提升,约是O-CN的1.6倍。光电流的增强意味着表面修饰SA-TCPP后,复合材料的光生载流子的分离效率得到显著改善,这对提高其光催化活性是有利的。如图9(b))所示,EIS图谱的弧半径可以反映电极表面的反应速率,较小的电弧半径意味着电荷转移的电阻较小。SA-TCPP/O-CN-40%的圆弧半径小于O-CN,这说明复合材料的异质结构中光生电子-空穴对的分离和迁移效率更高。证明本发明用原位法制备的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂的光生载流子分离和迁移能力显著提升,从而具有更加优异的可见光催化降解污染物和产氧性能。
图10为实施例1制备的SA-TCPP/O-CN与对比例1制备的O-CN、对比例2制备的SA-TCPP的PL对比图。如图10所示,在370nm激发波长下,O-CN表现出较强的荧光发射光谱,发射峰约位于454nm。与SA-TCPP复合后,SA-TCPP/O-CN复合材料的PL峰强度呈现降低趋势,呈现明显的荧光淬灭的现象,这表明O-CN与SA-TCPP之间存在有效的电子转移过程,因而光生电子-空穴对的复合几率显著降低。相较于O-CN,SA-TCPP/O-CN复合材料发射峰红移至489nm处,进一步说明了SA-TCPP和O-CN之间存在π-π相互作用,使得光生电荷能够进行有效地转移。证明本发明用原位法制备的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂的光生电子-空穴对的复合几率显著降低和光生电荷的迁移能力显著提升,从而具有更加优异的可见光催化降解污染物和产氧性能。
图11为对比例1制备的O-CN和对比例2制备的SA-TCPP的能带结构对比图。如图11(a)所示,带隙宽度根据DRS图以Tauc-Plot公式计算得,O-CN和SA-TCPP的带隙(Eg)值分别为2.31eV和1.78eV。如图11(b)所示,通过测定样品的MS曲线获得材料的半导体类型及平带的具体信息,O-CN与SA-TCPP的MS图呈现S型且斜率为正,表明两者均为n型半导体。根据Cs-2-0线性电位曲线交点计算得到O-CN和SA-TCPP的的平带电位(Efb)分别为-1.12V和-0.39V(vs.SCE),换算后得到O-CN和SA-TCPP的导带底部电位(ECB)分别为-1.08V和-0.35V(vs.NHE)。根据Eg和ECB结果,计算得O-CN和SA-TCPP的价带顶部电位(EVB)分别为1.23V和1.43V(vs.NHE)。由于O-CN和SA-TCPP的导带和价带位置交错,因此在两者间构建有效且稳定的II型异质结的方案是可行的。证明本发明用原位法制备的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂中O-CN与SA-TCPP间异质界面的存在可以形成内部电场,促进界面处光生电子-空穴对的分离和迁移,从而产生具有更加优异的可见光催化降解污染物和产氧性能。
Claims (7)
1.自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,其特征在于,所述光催化剂由自组装四(4-羧基苯基)卟啉和氧掺杂氮化碳纳米片通过静电作用和π-π相互作用复合而成,其中氧掺杂氮化碳纳米片和自组装四(4-羧基苯基)卟啉的质量比范围为1:0.1~0.6;所述自组装四(4-羧基苯基)卟啉通过原位法修饰到氧掺杂氮化碳纳米片上;所述光催化剂由以下方法制得:所述方法以3-氨基-1,2,4-三氮唑为原料,通过热刻蚀-水热相结合的方法制备氧掺杂氮化碳纳米片,通过自组装法制备四(4-羧基苯基)卟啉超分子,最后通过原位法将自组装四(4-羧基苯基)卟啉超分子修饰到氧掺杂氮化碳纳米片上;所述方法具体步骤为:
(1)以3-氨基-1,2,4-三氮唑为原料,在空气气氛下进行煅烧,制备得到块状氮化碳,再将块状氮化碳研磨后在空气气氛下进行二次煅烧,制备得到氮化碳纳米片,然后将氮化碳纳米片超声分散在过氧化氢水溶液中,并进行水热反应,反应完后冷却,进行固液分离收集沉淀,将沉淀干燥研磨成粉,制备得到氧掺杂氮化碳纳米片;
(2)将四(4-羧基苯基)卟啉分散于强碱溶液中进行加热搅拌,使得四(4-羧基苯基)卟啉完全溶解,形成四(4-羧基苯基)卟啉溶液;
(3)将步骤(1)中所得氧掺杂氮化碳纳米片超声分散在水中,加入步骤(2)中所得四(4-羧基苯基)卟啉溶液,进行搅拌超声混合,再加入强酸溶液进行加热搅拌,直至溶液pH变为中性,反应结束后进行固液分离收集沉淀,沉淀经洗涤干燥并研磨,即得自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂。
2.根据权利要求1所述的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,其特征在于,步骤(1)中所述煅烧包括依次进行的升温加热阶段和恒温阶段;所述升温加热阶段的升温速率为1~12 ℃/min;所述恒温阶段的温度为450~600 ℃,恒温时间为1~8 h;所述超声功率为200~800 W,超声频率为10~50 kHz,超声时间为5~60 min。
3.根据权利要求1所述的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,其特征在于,步骤(1)中所述过氧化氢水溶液的浓度为0.1~40 vol%,氮化碳与过氧化氢水溶液的质量体积比g/mL为1:30~150;所述水热反应温度为80~150 ℃,反应时间为2~10 h。
4.根据权利要求1所述的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,其特征在于,步骤(2)的反应体系中加入强碱溶液浓度为0.01~10 mol/L,所述四(4-羧基苯基)卟啉与强碱溶液的质量体积比g/mL为1:10~200,所述的强碱为氢氧化钾或氢氧化钠;所述加热反应的温度为50~150 ℃,反应时间为0.1~10 h。
5.根据权利要求1所述的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂,其特征在于,步骤(3)中所述氧掺杂氮化碳纳米片与水的质量体积比mg/mL为1:0.1~10;所述超声功率为200~800 W,超声频率为10~50 kHz,超声处理时间为0.1~5 h;所述氧掺杂氮化碳纳米片与自组装四(4-羧基苯基)卟啉的质量比为1:0.1~0.6,所述搅拌的反应时间为0.5~5 h;反应体系中加入强酸溶液浓度为0.01~10 mol/L,四(4-羧基苯基)卟啉与强酸的质量体积比g/mL为1:1~200,所述的强酸为盐酸、硫酸或硝酸;所述加热反应温度为30~150 ℃,搅拌的反应时间为0.1~10 h。
6.权利要求1所述的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂在污染物降解中的应用。
7.权利要求1所述的自组装四(4-羧基苯基)卟啉/氧掺杂氮化碳纳米片异质结光催化剂在光解水产氧中的应用。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105597820A (zh) * | 2015-12-24 | 2016-05-25 | 西北师范大学 | 一种类石墨相的氮化碳/四羧基苯基卟啉纳米复合材料及其制备方法 |
CN111389458A (zh) * | 2020-01-16 | 2020-07-10 | 江南大学 | 含羧基苝酰亚胺/氧掺杂氮化碳纳米片异质结光催化剂及其制备方法和应用 |
-
2020
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105597820A (zh) * | 2015-12-24 | 2016-05-25 | 西北师范大学 | 一种类石墨相的氮化碳/四羧基苯基卟啉纳米复合材料及其制备方法 |
CN111389458A (zh) * | 2020-01-16 | 2020-07-10 | 江南大学 | 含羧基苝酰亚胺/氧掺杂氮化碳纳米片异质结光催化剂及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
"From UV to NIR: A Full-Spectrum Metal-Free Photocatalyst for Efficient Polymer Synthesis in Aqueous Conditions";Stephanie Allison-Logan等;《Angew. Chem.》;20200915;第132卷;第21577页左栏第3段 * |
"类石墨相氮化碳复合材料光催化性能的研究";李文奇;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20190515(第5期);第23页第2段、第26页第2.2.3.3节、第29页第2.3.1节、第30页第2.3.3节、第32页第2.3.5节 * |
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