CN112844438B - 类红细胞状BiVO4/hm-C(CN)3Z型异质结及其制备方法和应用 - Google Patents
类红细胞状BiVO4/hm-C(CN)3Z型异质结及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种类红细胞状BiVO4/hm‑C(CN)3 Z型异质结及其制备方法和应用,该材料首先通过模板诱导结合水热法制备BiVO4,再在BiVO4骨架上原位包覆hm‑C(CN)3制备而成。将硝酸铋和偏钒酸铵分别溶于硝酸和氢氧化钠溶液中,再加入聚乙烯吡咯烷酮,随后将偏钒酸铵溶液滴加到硝酸铋溶液中,搅拌下用氢氧化钠溶液调节体系pH至中性,转移至高压釜中进行高温水热反应,得到尺度介于2‑3μm的类红细胞状BiVO4。将三氰基甲烷化咪唑离子液体吸附于BiVO4,高温聚合得到BiVO4/hm‑C(CN)3Z型异质结。本发明的类红细胞状BiVO4/hm‑C(CN)3 Z型异质结具有优异的CO2捕获、活化和光生电子、空穴分离能力,可应用于催化和能源转化领域。
Description
技术领域
本发明属于半导体复合材料技术领域,具体涉及一种类红细胞状BiVO4/hm-C(CN)3 Z型异质结及其制备方法。
背景技术
半导体光催化还原CO2技术被誉为是解决当前环境问题和能源危机的绿色有效方法,具有极大的研究价值和应用前景。自1979年Inoue T等首次报道了二氧化钛半导体材料应用于光电催化还原CO2的研究以来,国内外学者已经对光催化还原CO2的机理和产物选择性进行了广泛而深入的分析。然而,传统的二氧化钛等光催化剂因存在着禁带宽度较大,CO2吸附能力不足,可见光利用率低以及光生电子空穴复合率高等缺陷,其应用受到了极大的限制。作为一种多功能材料,钒酸铋(BiVO4)由于具有较高的可见光捕集能力和较正的价带电位,在光催化产氧和污染物降解方面得到了广泛的应用。该半导体材料制备工艺简单,化学稳定性好,无毒,在光催化领域具有广阔的应用前景。然而,单纯BiVO4能带位置较正,光生载流子复合率较高,导致其光催化效率不高,热别是难以实现CO2的还原转换。为了进一步改善BiVO4的物理及化学性质,通过元素掺杂以及与不同半导体材料进行复合,成为近年BiVO4材料的主要改性策略。
专利CN110038641A公开了一种钒酸铋/铬卟啉/石墨烯量子点二维复合Z型光催化材料及其光催化分解水产氢应用。该复合材料没有突出的形貌特征,同时需要石墨烯量子点(GOD)的负载作为电子传导介质。专利CN106944118A公开了一种金属Ag纳米颗粒沉积修饰的PCNS/BiVO4复合光催化剂,该催化剂通过水热反应得到钒酸铋负载的磷杂化石墨相氮化碳纳米片复合材料,再通过光照对含有硝酸银的甲基橙溶液进行Ag的还原沉积,制备工艺繁琐,且催化剂没有特殊的形貌结构,需要借助贵金属Ag的等离子体共振效应拓宽光子吸收范围和提升载流子分离效率。
发明内容
本发明的目的是提供一种类红细胞状BiVO4/hm-C(CN)3Z型异质结及其制备方法和应用,该异质结首先通过聚乙烯吡咯烷酮模板诱导结合水热法制备BiVO4,再在BiVO4骨架上原位包覆hm-C(CN)3制备而成。该材料制备工艺可控,具有较高的比表面积和良好的可见光响应性,特别是其优异的光生电子-空穴分离能力,使得材料在光催化降解污染物、水分解、CO2应用领域极具潜力。
实现本发明目的的技术解决方案是:一种类红细胞状BiVO4/hm-C(CN)3Z型异质结,该材料由三维空心骨架BiVO4以及半金属hm-C(CN)3包覆层共同构成,其中,三维空心骨架BiVO4由BiVO4纳米颗粒自组装形成,半金属hm-C(CN)3均匀包覆在三维空心骨架BiVO4表面,半金属hm-C(CN)3在Z型异质结中的含量为1.5-4 wt%。
进一步的,所述的类红细胞状BiVO4/hm-C(CN)3Z型异质结的尺度介于2-3 μm。
上述类红细胞状BiVO4/hm-C(CN)3Z型异质结的制备方法,其具体步骤为:
步骤1)剧烈搅拌下,将偏钒酸铵的分散液逐滴加入到硝酸铋的分散液中,搅拌0.5~1 h,调节pH至中性,继续搅拌0.5~1 h,然后将所得混合体系于200 ℃下水热反应3 h,自然冷却至室温,离心分离,洗涤,冷冻干燥,得到类红细胞状BiVO4;
步骤2)将类红细胞状BiVO4置于三氰基甲烷化咪唑离子液体的乙酸乙酯溶液中,超声处理30 min,旋蒸除去乙酸乙酯,在氮气气氛下,于400 ℃加热1 h,得到所述Z型异质结。
较佳的,步骤1)中,偏钒酸铵的分散液和硝酸铋的分散液中的分散剂均为聚乙烯吡咯烷酮,偏钒酸铵与硝酸铋的摩尔比为1:1;偏钒酸铵的分散液中偏钒酸铵的浓度为0.5mol/L,聚乙烯吡咯烷酮的浓度为25 g/L;硝酸铋的分散液中硝酸铋的浓度为0.5mol/L,聚乙烯吡咯烷酮的浓度为25 g/L。
较佳的,步骤1)中,偏钒酸铵的分散液通过在0.5 mol/L偏钒酸铵溶液中加入聚乙烯吡咯烷酮,搅拌一段时间后得到,其中,偏钒酸铵溶液为0.5 mol/L偏钒酸铵的氢氧化钠溶液。
较佳的,步骤1)中,硝酸铋的分散液通过在0.5 mol/L硝酸铋溶液中加入聚乙烯吡咯烷酮,搅拌一段时间后得到,其中,硝酸铋溶液为0.5 mol/L硝酸铋的硝酸溶液。
较佳的,步骤2)中,三氰基甲烷化咪唑离子液体的乙酸乙酯溶液的质量浓度为4g/L~10 g/L。
较佳的,步骤2)中,BiVO4和三氰基甲烷化咪唑离子液体的质量比为25:1~10:1。
所述的类红细胞状BiVO4/hm-C(CN)3 Z型异质结在光催化污染物降解、水分解和二氧化还原转换中的应用。
与现有技术相比,本发明的有益效果是:
(1)与常见的间接Z型异质结不同,将有机高分子半金属材料用于直接Z型异质结的构筑,无需任何电子传输介质,电子可以直接、高效到达催化反应活性位点,复合体系的电子-空穴分离效率更高。
(2)本发明的类红细胞状BiVO4/hm-C(CN)3 Z型异质结具有空心内腔,类红细胞结构由BiVO4纳米颗粒组装形成,半金属hm-C(CN)3均匀包覆在BiVO4骨架表面。空心内腔具有更大的比表面积,能够提高光子利用率,提升材料的吸附、传质能力,并提供更多的催化反应活性位点。
(3)半金属材料hm-C(CN)3电导率高,电子密度大,其优异的CO2吸附、活化和电子传输能力被同步整合入催化反应还原位点。
下面结合附图对本发明作进一步详细描述。
附图说明
图1 为类红细胞状BiVO4/hm-C(CN)3 Z型异质结的制备流程图。
图2 为实施例3所得类红细胞状BiVO4/hm-C(CN)3 Z型异质结的SEM照片。
图3 为对比例所得BiVO4/hm-C(CN)3 Z型异质结的SEM照片。
图4为实施例3所得类红细胞状BiVO4/hm-C(CN)3 Z型异质结的TEM照片。
图5为实施例3类红细胞状BiVO4/hm-C(CN)3 Z型异质结的XRD谱图。
图6为实施例3所得类红细胞状BiVO4/hm-C(CN)3 Z型异质结的FTIR谱图。
图7为实施例3所得类红细胞状BiVO4/hm-C(CN)3 Z型异质结的光催化CO2还原应用效率。
具体实施方式
下面的实施例可以使本专业技术人员更全面地理解本发明。
本发明的类红细胞状BiVO4/hm-C(CN)3直接接触型固态Z型异质结,BiVO4和hm-C(CN)3构成直接接触界面,无需任何电子传输介质,能够显著提升体系中两种半导体界面的电子迁移效率,加快光生电子和空穴对的分离。同时,三维类红细胞空心球结构不仅可以增加光子吸收利用率,而且有助于反应物的扩散传质。该Z型异质结将优异的二氧化碳捕获,活化和电荷传递功能集中整合到了还原反应位点,可实现CO2的高效光转化。与传统的Ⅱ型异质结相比,类红细胞状BiVO4/hm-C(CN)3 Z型异质结具有更强的氧化还原能力。
本发明所述的类红细胞状BiVO4/hm-C(CN)3Z型异质结的制备方法,其具体步骤为:
步骤a),将硝酸铋五水合物溶解于4 mol/L硝酸溶液中,搅拌处理10-30 min,得到均匀分散的0.5mol/L硝酸铋溶液;
步骤b),将与步骤a)中硝酸铋五水合物等摩尔量的偏钒酸铵溶解于2 mol/L氢氧化钠溶液中,搅拌处理10-30 min,得到均匀分散的0.5mol/L偏钒酸铵溶液;
步骤c),在剧烈搅拌下,向步骤a)得到的0.5mol/L硝酸铋溶液加入聚乙烯吡咯烷酮,搅拌处理30 min,得到均匀分散的硝酸铋分散液(混合液),其中,聚乙烯吡咯烷酮在硝酸铋分散液中的浓度为25 g/L;
步骤d),在剧烈搅拌下,向步骤b)得到的偏钒酸铵溶液加入聚乙烯吡咯烷酮,搅拌处理30 min,得到均匀分散的偏钒酸铵分散液(混合液),其中,聚乙烯吡咯烷酮在偏钒酸铵分散液中的浓度为25 g/L;
步骤e)剧烈搅拌下,将步骤d)所得偏钒酸铵分散液逐滴加入到步骤c)所得硝酸铋分散液中,在室温搅拌0.5~1 h,用2 mol/L氢氧化钠溶液调节pH至中性,继续搅拌0.5~1h,然后将所得混合体系于200 ℃下水热反应3 h,自然冷却至室温,离心分离,洗涤,冷冻干燥,得到类红细胞状BiVO4;
步骤f)将三氰基甲烷化咪唑离子液体溶解于乙酸乙酯中,得到质量浓度为4 g/L~10 g/L的三氰基甲烷化咪唑离子液体的乙酸乙酯溶液,然后将步骤e)得到的类红细胞状BiVO4分散到其中,超声处理30 min,旋蒸除去乙酸乙酯,在氮气气氛下400 ℃加热1 h,得到类红细胞状BiVO4/hm-C(CN)3 Z型异质结,BiVO4和三氰基甲烷化咪唑离子液体的质量比为25:1~10:1。
对比例
5.0 mmol(2.45 g)Bi(NO3)3·5H2O和 5.0 mmol(0.58 g)的NH4VO3分别溶解于10.0mL 的HNO3溶液(4.0 mol/L)和10.0 mL的NaOH溶液(2.0 mol/L)中。形成均一的溶液后,将0.125 g聚乙烯吡咯烷酮(PVP)分别加入到上述两种溶液中,搅拌0.5小时。在剧烈搅拌下,将NH4VO3溶液缓慢地滴加Bi(NO3)3·5H2O溶液中,然后用2 mol/L NaOH溶液将混合溶液的pH值调节至7.0,并搅拌0.5小时。随后将该混合溶液转移到水热釜中,以2 ℃/min速率升温至200 ℃,保温3个小时。待溶液自然冷却后,离心,再分别用蒸馏水和无水乙醇反复洗涤3次,冷冻干燥后得到类红细胞状的中空BiVO4。将0.1 g三氰基甲烷化咪唑离子液体溶解于10mL乙酸乙酯中,随后将1 g的类红细胞状BiVO4分散到其中,超声处理30 min,旋蒸除去乙酸乙酯,在氮气气氛下400 ℃加热1 h,得到类红细胞状BiVO4/hm-C(CN)3 Z型异质结。
图3为上述制备方法得到的BiVO4/ hm-C(CN)3 Z型异质结的SEM照片,由图可观察到,材料无类红细胞状空心球结构,只有少许的平均直径在2-3 μm的实心球结构,这可能是由于加入的结构导向剂聚乙烯吡咯烷酮(PVP)的量过少,导致BiVO4颗粒无法规律、有序自组装。
实施例1
5.0 mmol(2.45 g)Bi(NO3)3·5H2O和 5.0 mmol(0.58 g)的NH4VO3分别溶解于10.0mL 的HNO3溶液(4.0 mol/L)和10.0 mL的NaOH溶液(2.0 mol/L)中。形成均一的溶液后,将0.25 g聚乙烯吡咯烷酮(PVP)分别加入到上述两种溶液中,搅拌0.5小时。在剧烈搅拌下,将NH4VO3溶液缓慢地滴加Bi(NO3)3·5H2O溶液中,然后用2 mol/L NaOH溶液将混合溶液的pH值调节至7.0,并搅拌0.5小时。随后将该混合溶液转移到水热釜中,以2 ℃/min速率升温至200℃,保温3个小时。待溶液自然冷却后,离心,再分别用蒸馏水和无水乙醇反复洗涤3次,冷冻干燥后得到类红细胞状的中空BiVO4。将0.1 g三氰基甲烷化咪唑离子液体溶解于10mL乙酸乙酯中,随后将1 g的类红细胞状BiVO4分散到其中,超声处理30 min,旋蒸除去乙酸乙酯,在氮气气氛下400 ℃加热1 h,得到类红细胞状BiVO4/hm-C(CN)3 Z型异质结。
实施例2
5.0 mmol(2.45 g)Bi(NO3)3·5H2O和 5.0 mmol(0.58 g)的NH4VO3分别溶解于10.0mL 的HNO3溶液(4.0 mol/L)和10.0 mL的NaOH溶液(2.0 mol/L)中。形成均一的溶液后,将0.25 g聚乙烯吡咯烷酮(PVP)分别加入到上述两种溶液中,搅拌0.5小时。在剧烈搅拌下,将NH4VO3溶液缓慢地滴加Bi(NO3)3·5H2O溶液中,然后用2 mol/L NaOH溶液将混合溶液的pH值调节至7.0,并搅拌0.5小时。随后将该混合溶液转移到水热釜中,以2 ℃/min速率升温至200℃,保温3个小时。待溶液自然冷却后,离心,再分别用蒸馏水和无水乙醇反复洗涤3次,冷冻干燥后得到类红细胞状的中空BiVO4。将0.067 g三氰基甲烷化咪唑离子液体溶解于10mL乙酸乙酯中,随后将1 g的类红细胞状BiVO4分散到其中,超声处理30 min,旋蒸除去乙酸乙酯,在氮气气氛下400 ℃加热1 h,得到类红细胞状BiVO4/hm-C(CN)3 Z型异质结。
实施例3
5.0 mmol(2.45 g)Bi(NO3)3·5H2O和 5.0 mmol(0.58 g)的NH4VO3分别溶解于10.0mL 的HNO3溶液(4.0 mol/L)和10.0 mL的NaOH溶液(2.0 mol/L)中。形成均一的溶液后,将0.25 g聚乙烯吡咯烷酮(PVP)分别加入到上述两种溶液中,搅拌0.5小时。在剧烈搅拌下,将NH4VO3溶液缓慢地滴加Bi(NO3)3·5H2O溶液中,然后用2 mol/L NaOH溶液将混合溶液的pH值调节至7.0,并搅拌0.5小时。随后将该混合溶液转移到水热釜中,以2 ℃/min速率升温至200℃,保温3个小时。待溶液自然冷却后,离心,再分别用蒸馏水和无水乙醇反复洗涤3次,冷冻干燥后得到类红细胞状的中空BiVO4。将0.05 g三氰基甲烷化咪唑离子液体溶解于10mL乙酸乙酯中,随后将1 g的类红细胞状BiVO4分散到其中,超声处理30 min,旋蒸除去乙酸乙酯,在氮气气氛下400 ℃加热1 h,得到类红细胞状BiVO4/hm-C(CN)3 Z型异质结。
图2为类红细胞状BiVO4/ hm-C(CN)3 Z型异质结的SEM照片,由图可观察到,类红细胞状结构由BiVO4颗粒组装形成,其分散性良好,平均直径在2-3 μm。无定形半金属hm-C(CN)3包覆在BiVO4表面上,其中hm-C(CN)3的含量在2 wt%左右。
图4为类红细胞状BiVO4/ hm-C(CN)3 Z型异质结的TEM照片,如图所示,由深色边缘和浅色中心的对比可知类红细胞状BiVO4/ hm-C(CN)3 Z型异质结具有空心结构。在类红细胞状BiVO4/ hm-C(CN)3 Z型异质结的表面及空腔内部具有许多纳米颗粒,为BiVO4的纳米颗粒。
图5为类红细胞状BiVO4/ hm-C(CN)3 Z型异质结的XRD谱图,图中BiVO4的各个衍射峰与标准BiVO4四方晶型(PDF 14-0133)的衍射峰几乎完全一致,半金属hm-C(CN)3在26.1°出现一个特征衍射峰,对应于(002)晶面,由此证明BiVO4与hm-C(CN)3成功复合。
图6为类红细胞状BiVO4/hm-C(CN)3 Z型异质结的FTIR谱图,在1576cm-1、1000-1500 cm-1和661 cm-1三处出现了吸收带。其中在1576cm-1的吸收峰对应于半金属hm-C(CN)3的C=N伸缩振动,1000-1500 cm-1的区域显示出CN杂环的伸缩振动特征峰,在661 cm-1处的吸收峰为半金属hm-C(CN)3的C-(C)3拉伸振动峰, 680 cm-1处的吸收峰对应于BiVO4结构中的Bi-O键。
图7为类红细胞状BiVO4/ hm-C(CN)3 Z型异质结的光催化CO2还原性能表征,实验采用300W氙灯作为光源。从图中可以看到,类红细胞状BiVO4/ hm-C(CN)3 Z型异质结具有较好的催化活性,经6个小时光照,CO产量达到244.8 μmol·g-1。
实施例4
5.0 mmol(2.45 g)Bi(NO3)3·5H2O和 5.0 mmol(0.58 g)的NH4VO3分别溶解于10.0mL 的HNO3溶液(4.0 mol/L)和10.0 mL的NaOH溶液(2.0 mol/L)中。形成均一的溶液后,将0.25 g聚乙烯吡咯烷酮(PVP)分别加入到上述两种溶液中,搅拌0.5小时。在剧烈搅拌下,将NH4VO3溶液缓慢地滴加Bi(NO3)3·5H2O溶液中,然后用2 mol/L NaOH溶液将混合溶液的pH值调节至7.0,并搅拌0.5小时。随后将该混合溶液转移到水热釜中,以2 ℃/min速率升温至200℃,保温3个小时。待溶液自然冷却后,离心,再分别用蒸馏水和无水乙醇反复洗涤3次,冷冻干燥后得到类红细胞状的中空BiVO4。将0.04 g三氰基甲烷化咪唑离子液体溶解于10mL乙酸乙酯中,随后将1 g的类红细胞状BiVO4分散到其中,超声处理30 min,旋蒸除去乙酸乙酯,在氮气气氛下400 ℃加热1 h,得到类红细胞状BiVO4/hm-C(CN)3 Z型异质结。
Claims (9)
1.一种类红细胞状BiVO4/hm-C(CN)3Z型异质结,其特征在于,由三维空心骨架BiVO4以及半金属hm-C(CN)3包覆层共同构成,其中,三维空心骨架BiVO4由BiVO4纳米颗粒自组装形成,半金属hm-C(CN)3均匀包覆在三维空心骨架BiVO4表面,半金属hm-C(CN)3在Z型异质结中的含量为1.5-4 wt%。
2.如权利要求1所述的Z型异质结,其特征在于,所述的Z型异质结的尺度介于2-3 μm。
3.如权利要求1或2所述的Z型异质结的制备方法,其特征在于,其具体步骤为:
步骤1)剧烈搅拌下,将偏钒酸铵分散液逐滴加入到硝酸铋分散液中,搅拌0.5~1 h,调节pH至中性,继续搅拌0.5~1 h,然后将所得混合体系于200 ℃下水热反应3 h,自然冷却至室温,离心分离,洗涤,冷冻干燥,得到类红细胞状BiVO4;
步骤2)将类红细胞状BiVO4置于三氰基甲烷化咪唑离子液体的乙酸乙酯溶液中,超声处理30 min,旋蒸除去乙酸乙酯,在氮气气氛下,于400 ℃加热1 h,得到所述Z型异质结;
其中,偏钒酸铵分散液和硝酸铋分散液中的分散剂均为浓度为 25 g/L的聚乙烯吡咯烷酮。
4.如权利要求3所述的方法,其特征在于,步骤1)中,偏钒酸铵与硝酸铋的摩尔比为1:1;偏钒酸铵分散液中偏钒酸铵的浓度为0.5mol/L;硝酸铋分散液中硝酸铋的浓度为0.5mol/L。
5.如权利要求3所述的方法,其特征在于,步骤1)中,偏钒酸铵分散液通过在0.5 mol/L偏钒酸铵溶液中加入聚乙烯吡咯烷酮,搅拌一段时间后得到,其中,偏钒酸铵溶液为0.5mol/L偏钒酸铵的氢氧化钠溶液。
6.如权利要求3所述的方法,其特征在于,步骤1)中,硝酸铋分散液通过在0.5 mol/L硝酸铋溶液中加入聚乙烯吡咯烷酮,搅拌一段时间后得到,其中,硝酸铋溶液为0.5 mol/L硝酸铋的硝酸溶液。
7.如权利要求3所述的方法,其特征在于,步骤2)中,三氰基甲烷化咪唑离子液体的乙酸乙酯溶液的质量浓度为4 g/L~10 g/L。
8.如权利要求3所述的方法,其特征在于,步骤2)中,BiVO4和三氰基甲烷化咪唑离子液体的质量比为25:1~10:1。
9.如权利要求1或2所述的Z型异质结在光催化污染物降解、水分解或二氧化碳还原转换中的应用。
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