CN112717974B - 一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂 - Google Patents
一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及一种高效光催化裂解水制氢的磷(P)掺杂超薄空心氮化碳纳米 球(UH-CNS)催化剂。本发明以氰胺和红磷为前驱体,利用负压超声法和化学 气相沉积法分别制备了空心氮化碳纳米球(H-CNS)和磷掺杂的超薄空心氮化 碳纳米球(P/UH-CNS),最终实现高效的光催化裂解水制氢。属于催化化学与 纳米科学领域。
背景技术
21世纪以来,随着社会和经济的迅猛发展,工业经济对于化石能源的过度 依赖致使地球蕴藏的化石燃料不断被消耗,能源危机与环境污染已成为全球的 焦点。太阳能是一种取之不尽用之不竭的可再生能源,同时氢能也具有清洁、 安全环保、能量密度高等优点,被视为是可以取代传统矿石能源的新能源。受 自然界光合作用启发,利用光催化剂直接吸收太阳能将水解离,制备清洁的氢 能并储存利用,为解决能源枯竭和环境问题提供了新途径。尽管研究光催化裂 解水制氢已有30多年的历史,并取得了较快的发展,但总体仍处在理论探索和 实验室阶段,很多实际问题有待解决,距离工业化应用还有一定的距离。目前主要存在的问题包括:(1)催化剂比表面积较低;(2)对可见光响应较弱; (3)电荷复合速率较高。因此,研究和开发在可见光范围内具有较高光催化活 性的半导体材料是实现太阳能制氢的关键。
在众多半导体光催化剂中,氮化碳(g-C3N4)是其中较为经典的非金属光催 化剂,具有优异的制氢活性。然而,低比表面积、光生电子-空穴对的低分离效 率和较弱的可见光响应能力极大限制了体相g-C3N4材料的实际应用。研究表明, 可通过形貌调控、掺杂、光敏化、异质结构建等方式有效提升g-C3N4的光催化 活性。本发明首先利用负压超声法制备了具有大比表面积的空心氮化碳纳米球, 其中空结构可促进电子和空穴分别向纳米球内外表面的还原中心和氧化中心迁 移,从而实现电荷的局域化,提高量子产率。接着,选用无毒、价格低廉的单 质红磷作为磷源,通过一步化学气相沉积法制备了磷掺杂的超薄空心氮化碳纳 米球。制备过程中,磷蒸汽在空心氮化碳纳米球内外表面形成的压力差,可使 原本疏松的空心氮化碳纳米球壳层变薄。另外,磷元素的掺杂可显著优化空心 氮化碳纳米球的电子结构和表面性质,降低光生电荷的复合速率,从而提升材 料整体的光解水制氢活性。
同时经文献调研发现,目前尚无此类磷掺杂超薄空心氮化碳纳米球催化剂 的制备及其应用于光催化裂解水制氢的报道。因此,本文首次以红磷作为磷源, 利用改进的化学气相沉积法制备了一系列x wt%P/UH-CNS(x=0-10)光催化 剂,实现了此类催化剂材料的可控制备,同时研究发现2wt%P/UH-CNS催化剂 具有最佳的光催化裂解水制氢活性。
发明内容
本发明的目的在于利用化学气相沉积法制备x wt%P/UH-CNS(x=0-10) 催化剂,用于高效的光催化裂解水制氢。
一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂,其特 征在于,为薄壁空心球状氮化碳,且氮化碳球壁掺有P,P的掺杂量为x wt%, x=0-10且不为0。
进一步优选球壁的厚度为20-30nm;空心球的内直径为400-600nm。进一步 球壁上还有孔。
所述磷掺杂超薄空心氮化碳纳米球催化剂的制备方法,其特征在于,包括 以下步骤:
(1)制备表面一层带介孔内部实心的核壳球状SiO2模板;
(2)采用负压超声法制备空心氮化碳纳米球(H-CNS),将步骤(1)所得 的核壳球状SiO2模板在抽真空且同时伴有超声的条件下吸附负载氰胺,然后煅 烧,再用NH4HF2去除SiO2模板,得到空心氮化碳纳米球(H-CNS);
(3)采用化学气相沉积法制备磷掺杂超薄空心氮化碳纳米球,空心氮化碳 纳米球(H-CNS)、碘和纯化后的红磷添加到石英安瓿瓶中,抽真空并用乙炔火 焰密封;然后将上述石英管以2℃/min的速率加热到420-480℃,保温3-5h; 以1℃/min的速率冷却到260-300℃,保温3-5h;接着以0.2℃/min的速率缓 慢冷却至室温;最后,将所制备的样品用CS2、蒸馏水和乙醇洗涤,干燥得到x wt%P/UH-CNS(x=0-10)催化剂。
H-CNS粉末与碘的质量比为100:(0.5-1.5),P根据掺杂量调节。
本发明所得磷掺杂超薄空心氮化碳纳米球催化剂的应用,用于光催化分解 水制备氢气,具体步骤:将催化剂、水、三乙醇胺、Pt混合在可见光或太阳光 照射下制氢气。
本发明具有制备工艺简单、原料价格便宜、产量较高且产物形貌规整等特 征。本发明制备得到的x wt%P/UH-CNS催化剂对光催化裂解水制氢表现出优异 的活性和稳定性,其中活性最好的2wt%P/UH-CNS催化剂在模拟太阳光和可见 光下的产氢活性分别达到9653和2814μmol h-1g-1(测试条件:20mg催化剂, 45mL水,5mL三乙醇胺和2wt%Pt)。
附图说明
图1为所制得催化剂的XRD谱图。
图2为所制得催化剂的TEM照片。图中依次为(a,b)H-CNS,(c,d)1 wt%P/UH-CNS,(e,f)2wt%P/UH-CNS,(g,h)5wt%P/UH-CNS和(l,i)10 wt%P/UH-CNS催化剂的TEM照片。
图3为模拟太阳光(a)及可见光(b)下催化剂的制氢活性图。催化剂在 反应溶液中组成为:20mg催化剂,45mL水,5mL三乙醇胺和2wt%Pt。
具体实施方式
为了进一步阐述本发明,下面以实施例作详细说明,并给出附图描述本发 明得到的各催化剂材料。
实施例1:根据法合成SiO2模板。具体过程为:在35℃下,将9mL 氨水加入到150mL乙醇和20mL去离子水的混合液中,磁力搅拌1h,得到透 明前驱体溶液;在剧烈搅拌下将11mL正硅酸四乙酯(TEOS)快速加入到上述 前驱体溶液中,静置1h以获得白色悬浮液;然后,在剧烈搅拌下,将12.5mL 正硅酸四乙酯(TEOS)和6mL十八烷基三甲氧基硅烷(C18TMOS)的混合液 逐滴加入到上述悬浮液中,并在室温下静置3h;将所得反应液离心,干燥和焙烧,焙烧程序为:以5℃/min的速率由室温升至550℃,保温6h,然后冷却到 室温,得到白色固体;将上述样品在80℃下用1M HCl溶液酸化24h;最后经 离心、干燥,得到核壳SiO2模板。
实施例2:采用负压超声法制备空心氮化碳纳米球(H-CNS)。具体步骤如 下:将1gSiO2模板和5mL氰胺在一个连接真空管的耐压瓶中混合,并先后于 60℃下超声处理3h,80℃下磁力搅拌3h;然后将样品干燥并置于管式炉中焙 烧,焙烧程序为:N2氛围下,以5℃/min的速率由室温升至550℃,保温2h, 最后冷却到室温即制得黄色样品;将研磨后的样品用4M NH4HF2室温处理12h 去除SiO2模板;离心并用蒸馏水和乙醇洗涤,在60℃下干燥得到空心氮化碳 纳米球(H-CNS)。
实施例3:采用化学气相沉积法制备磷掺杂超薄空心氮化碳纳米球(x wt%P/UH-CNS,x=0-10)催化剂。具体步骤如下:将300mg H-CNS粉末、3mg 碘和一定量(1-10wt%)纯化后的红磷添加到石英安瓿瓶中,抽真空并用乙炔火 焰密封;然后将上述石英管以2℃/min的速率加热到450℃,保温4h;以1℃/min 的速率冷却到280℃,保温4h;接着以0.2℃/min的速率缓慢冷却至室温;最 后,将所制备的样品用CS2,蒸馏水和乙醇洗涤,在60℃下干燥得到x wt%P/UH-CNS(x=0-10)催化剂。
本发明具有制备工艺简单,原料价格便宜,产量较高且产物形貌规整、可 控等特点,本发明制备得到的2wt%P/UH-CNS催化剂表现出了优异的光催化裂 解水制氢活性。
Claims (7)
1.一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂,其特征在于,为薄壁空心球状氮化碳,且氮化碳球壁掺有P,P的掺杂量为x wt%,x=0-10且不为0;
高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂制备方法,包括以下步骤:
(1)制备表面一层带介孔内部实心的核壳球状SiO2模板;
(2)采用负压超声法制备空心氮化碳纳米球(H-CNS),将步骤(1)所得的核壳球状SiO2模板在抽真空且同时伴有超声的条件下吸附负载氰胺,然后煅烧,再用NH4HF2去除SiO2模板,得到空心氮化碳纳米球(H-CNS);
(3)采用化学气相沉积法制备磷掺杂超薄空心氮化碳纳米球,空心氮化碳纳米球(H-CNS)、碘和纯化后的红磷添加到石英安瓿瓶中,抽真空并用乙炔火焰密封;然后将上述石英安瓿瓶以2℃/min的速率加热到420-480℃,保温3-5h;以1℃/min的速率冷却到260-300℃,保温3-5h;接着以0.2℃/min的速率缓慢冷却至室温;最后,将所制备的样品用CS2、蒸馏水和乙醇洗涤,干燥得到xwt%P/UH-CNS催化剂。
2.按照权利要求1所述的一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂,其特征在于,球壁的厚度为20-30nm;空心球的内直径为400-600nm。
3.按照权利要求1所述的一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂,其特征在于,球壁上还有孔。
4.权利要求1-3任一项所述的一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂的制备方法,其特征在于,包括以下步骤:
(1)制备表面一层带介孔内部实心的核壳球状SiO2模板;
(2)采用负压超声法制备空心氮化碳纳米球(H-CNS),将步骤(1)所得的核壳球状SiO2模板在抽真空且同时伴有超声的条件下吸附负载氰胺,然后煅烧,再用NH4HF2去除SiO2模板,得到空心氮化碳纳米球(H-CNS);
(3)采用化学气相沉积法制备磷掺杂超薄空心氮化碳纳米球,空心氮化碳纳米球(H-CNS)、碘和纯化后的红磷添加到石英安瓿瓶中,抽真空并用乙炔火焰密封;然后将上述石英安瓿瓶以2℃/min的速率加热到420-480℃,保温3-5h;以1℃/min的速率冷却到260-300℃,保温3-5h;接着以0.2℃/min的速率缓慢冷却至室温;最后,将所制备的样品用CS2、蒸馏水和乙醇洗涤,干燥得到xwt%P/UH-CNS催化剂。
5.按照权利要求4所述的制备方法,其特征在于,H-CNS粉末与碘的质量比为100:(0.5-1.5),P根据掺杂量调节。
6.权利要求1-3任一项所述的一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂的应用,用于光催化分解水制备氢气。
7.权利要求6所述的一种高效光催化裂解水制氢的磷掺杂超薄空心氮化碳纳米球催化剂的应用,具体步骤:将催化剂、水、三乙醇胺、Pt混合在可见光或太阳光照射下制氢气。
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