CN115282961A - 一种以氧化铟为载体负载银的光催化剂及其制备方法和应用 - Google Patents
一种以氧化铟为载体负载银的光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种以氧化铟为载体负载银的光催化剂及其制备方法和应用,其是通过沉积沉淀法将Ag负载在具有光吸收的In2O3半导体载体上而制得所述负载型光催化剂。本发明中所得Ag/In2O3光催化剂在室温氙灯光照下对甲烷无氧偶联体系具有较高的甲烷转化率,其制备方法简单易行,在光催化甲烷转化方面具有较好的应用前景。
Description
技术领域
本发明属于能源利用及环境保护领域,具体是涉及以氧化铟为载体负载银的光催化剂及其制备方法和应用,该负载型催化剂可通过紫外可见光照射实现室温下高效光催化甲烷转化到乙烷和氢气,并具有良好的活性与稳定性,为光催化甲烷转化提供了一种新的思路。
背景技术
随着全球原油资源消耗的增加,而可燃冰和页岩气开采技术的迅速发展,甲烷的储量逐年增加,利用甲烷代替石油作为化学合成的基石,减少对原油的依赖提供了可能性。因此,甲烷作为一种清洁能源,同时也是作为大宗化学品的原料越来越受到人们的关注。根据2018年BP世界能源统计年鉴,全球天然气的储量高达190万亿平方米。近年来,荷兰一家公司以天然气形式生产的能源比原油还多。然而,由于甲烷分子具有十分稳定的成键结构,传统的甲烷转化技术(尤其是甲烷水汽重整反应)通常在高温条件下进行,需要大量的能量消耗,增加了该过程的经济成本和环境压力。在如此恶劣的反应条件下,经常会发生焦炭的快速堆积和催化剂的烧结,从而导致催化剂失活。而甲烷直接转化为高附加值的化学品如甲醇,但是低产率和低选择性(易深度氧化到CO2)。因此开发新的甲烷转化技术以提高转化效率和降低成本显得非常迫切。太阳能作为最丰富和最清洁的可再生能源,可用于在温和条件下驱动甲烷转化。光催化技术可以利用高能量的光生载流子来打破甲烷转化的热力学势垒并降低活化能,反应产生的热量也可以很容易消散,从而避免催化剂高温失活等缺陷,拓展出全新的反应路线,使传统热力学上不允许的反应可以在温和条件下通过光催化甲烷转化得到等比例乙烷和氢气产物的可能性。
光催化甲烷无氧偶联主要发生如下反应:2CH4→C2H6 + H2。NOCM反应将甲烷转化为具有高附加值的乙烷和清洁能源氢气。近些年来,金属氧化物材料(如TiO2,ZnO,Ga2O3等)由于其具有很强的氧化能力被广泛用于甲烷转化领域。但目前仍然面临着甲烷转化率低和产物选择性低的问题。因此,提高光催化低温氧化甲烷反应活性、产物选择性以及加深对甲烷C-H活化机理的理解对于甲烷转化有着重要的意义。
氧化铟(In2O3)作为n型宽带隙半导体,具有较低的电子亲和势、导电性较好和化学稳定性高等特点,已被广泛应用于光电领域、气体传感、发光二极管等方面,在光催化领域也显示出良好的发展前景。目前,在光催化甲烷无氧偶联的体系还没相关氧化铟材料的工作报道与应用。从氧化铟的能带结构考虑,其导带电势能够产氢,价带对应的氧化能力能够氧化甲烷,表明载体In2O3具有高的光氧化甲烷实现高转化率的能力。而从甲烷的吸附活化角度出发,甲烷能够吸附在金属氧化物的表面,改变催化剂的电子结构,有利于甲烷的吸附活化;Ag作为一种助剂不仅促进载流子的分离,也是能够促进甲基物种脱附的贵金属。因此本发明尝试采用In2O3负载Ag催化剂用于光催化甲烷无氧偶联。
发明内容
针对现有已报道用于甲烷无氧偶联催化剂的活性不高且产物选择性低的问题,本发明提供了一种氧化铟为载体负载银的负载型催化剂的制备方法和应用,该方法简单快速,且制得的Ag/In2O3催化剂具有较高的光催化甲烷无氧偶联的活性和产物选择性,为后续的催化剂设计提供一种思路,具有较好的应用前景。
为实现上述目的,本发明采用如下技术方案:
一种以氧化铟为载体负载银的光催化剂,其是以氧化铟为载体,银为主要活性组分构成的高分散负载型低温光催化剂;其中,主要活性组分银的含量为1.0-5.0 wt%,其余为氧化铟载体。
如上所述光催化剂在室温和氙灯照射下,能够实现450.26 μmol•g-1•h-1的乙烷产率和367.57 μmol•g-1•h-1氢气产率。
如上所述的以氧化铟为载体负载银的光催化剂的制备方法,采用InCl3和氨水作为原料得到氢氧化物前驱体后通过水洗、煅烧得到氧化铟载体;再利用沉积沉淀法在所得氧化铟载体上负载活性组分银。具体制备步骤如下:
(1)3.6 g InCl3溶解在含有54 mL的无水乙醇和18 mL的去离子水中,另外一个烧杯中装有54 mL无水乙醇和18 mL氨水(25~28 wt%)。两个溶液快速混合放入预热好的80℃水浴中,搅拌15 min,冷却至室温,去离子水洗涤5次,冷冻干燥6 h,在马弗炉中250℃煅烧3h制得In2O3载体;
(2)将上述制得的0.5 g In2O3载体溶解在50 mL H2O,加入2 mL AgNO3,搅拌1 h,加入过量的Na2CO3溶液(1 g溶于10 mL水),在80℃下水浴3 h,冷却至室温,去离子水洗涤,60℃真空干燥过夜。
其中,AgNO3溶液浓度为5 mg·mL-1。
所述的负载型Ag催化剂用于室温下光催化甲烷转化。所得Ag/ In2O3催化剂在室温紫外可见光照射下,其制备方法简单方便可行,为室温条件下光催化甲烷转化研究提供了一种新的思路。
本发明的显著优点在于:
载体氧化铟的导带电位低于氢标准电极,从而能够还原质子氢到氢气,且价带电位稍正与CH4/CH3氧化电位,避免甲烷的过度氧化到二氧化碳,通过负载Ag后高度分散于载体氧化铟上,Ag/In2O3催化剂形成表面蓬松多孔的结构且比表面积增大,有利于甲烷的吸附,将其应用于甲烷转化的光催化反应体系,该催化剂相比于已报道的用于甲烷无氧偶联催化剂的活性具有更加优异的的活性(见表1)。甲烷无氧偶联的反应机理是首先氧化铟载体吸附甲烷分子,引入光照后产生光生电子空穴对,催化剂的电子转移到甲烷分子从而活化甲烷,空穴将甲烷的第一个碳氢键断裂形成甲基物种,甲基物种转移到银的表面,吸附在银上的甲基物种再脱附到气相中形成甲基自由基,随后偶联形成乙烷,而光生电子将质子氢还原成氢气。本发明Ag/In2O3催化剂将难以储存的太阳能和难以转化的甲烷分子转化为易储存、易利用的化学燃料或化工原材料,开辟了In2O3材料新的应用方向,对于甲烷无氧偶联体系实现了产物高活性和选择性,催化剂制备方法简单快速,有利于对甲烷转化的反应机制提供一种新的思路,这也为太阳能的转化利用开辟了一种新的途径。
附图说明
图1为实施例1所得2 wt% Ag/ In2O3的XRD图;
图2为实施例1所得2 wt% Ag/ In2O3的紫外-漫反射光谱图;
图3为实施例1所得2 wt% Ag/ In2O3的TEM图;
图4为实施例1所得2 wt% Ag/ In2O3的BET图;
图5为实施例1所得2 wt% Ag/ In2O3的光催化CH4氧化性能图。
具体实施方式
为让本发明的上述特征和优点能更明显易懂,下文特举实施例,并配合附图,作详细说明如下,但本发明并不限于此。
实施例1
2 wt% Ag/ In2O3催化剂的制备
(1)3.6 g InCl3溶解在含有54 mL的无水乙醇和18 mL的去离子水中,另外一个烧杯中装有54 mL无水乙醇和18 mL氨水(25~28 wt%)。两个溶液快速混合放入预热好的80℃水浴中,搅拌15 min,冷却至室温,去离子水洗涤5次,冷冻干燥6 h,在马弗炉中250℃煅烧3h制得In2O3载体;
(2)将上述制得的0.5 g In2O3载体溶解在50 mL H2O,加入2 mL AgNO3溶液,搅拌1h,加入过量的Na2CO3溶液(1 g溶于10 mL水),在80℃下水浴3 h,冷却至室温,去离子水洗涤,60℃真空干燥过夜。
其中,AgNO3溶液浓度为5 mg·mL-1。
实施例2
催化剂的性能评价
催化剂的性能评价是在间歇式反应器进行,容积为175 mL,上方为石英玻璃,可透光照射到催化剂表面。反应前通过真空泵将装置抽真空,另一端连着反应气CH4,反应条件为:室温大气压条件下,催化剂质量20 mg,300 W氙灯作为光源,每间隔1 h通过微型进样针抽取反应体系中1 mL气体进入气相色谱检测产物。各产物的物质的量通过外标法换算得到,乙烷的选择性用如下公式计算:
C2H6 selectivity=n(C2H6)/{ n(C2H6)+ n(CO2)+ n(CO)}
这里n(C2H6)、n(CO)和n(CO2)分别指生成C2H6、CO和CO2的物质的量。
图1为所得In2O3和2 wt% Ag/ In2O3催化剂的XRD图。从图1中可以看出,由于Ag负载量较低,使得催化剂的XRD谱图中未出现与Ag有关的衍射锋,这也说明了催化剂中Ag粒子的均匀分散且没有影响In2O3的晶型结构。
图2为所得In2O3和2 wt% Ag/ In2O3催化剂的紫外-可见漫反射光谱图。从图2中可以看出,催化剂载体In2O3在紫外可见光区有光吸收,负载Ag后,由于Ag的局域表面等离子共振效应,该催化剂对可见光的吸收增强,说明负载后的催化剂能更好地利用可见光,发挥其光促作用。
图3为所得2 wt% Ag/ In2O3催化剂的透射电子显微镜图。从图3可以看出,该催化剂呈现薄片状形貌。
图4为所得负载物2 wt% Ag/ In2O3的BET图。从图4可以看出,Ag/ In2O3属于介孔材料,且具有较大的比表面积和孔容,有助于提高活性组分Ag的负载量和提供更多的活性中心,从而提高甲烷的活性。
图5为所得2 wt% Ag/ In2O3催化剂的CH4氧化活性图。从图5可以看出,随着反应时间的延长,目标产物乙烷和氢气的产率也在逐渐增加,同时乙烷选择性可达88%,这体现了该催化剂在紫外可见光下的优异活性和选择性。与其他载体催化剂相比,Ag/In2O3具有更高的乙烷产率(见表1)。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (6)
1.一种以氧化铟为载体负载银的光催化剂,其特征在于:所述的光催化剂是以In2O3为载体,Ag为活性组分的高分散负载型催化剂。
2.根据权利要求1所述的以氧化铟为载体负载银的光催化剂,其特征在于:所述的光催化剂中活性组分Ag的含量为1.0-5.0 wt%,其余为In2O3载体。
3.一种如权利要求1-2任一项所述的以氧化铟为载体负载银的光催化剂的制备方法,其特征在于:以氯化铟为前驱体合成In2O3载体,再利用沉积沉淀法在所得In2O3载体上负载活性组分Ag。
4.根据权利要求3所述的制备方法,其特征在于:具体包括以下步骤:
(1)先将InCl3溶解在含有无水乙醇和去离子水,再将无水乙醇和25~28 wt%的氨水混合,然后将两种混合液保持3:1的体积比快速混合并转移到80℃水浴中,搅拌15 min,离心,去离子水洗涤5次,冷冻干燥6 h,在马弗炉中250℃煅烧3 h制得In2O3载体;
(2)在步骤(1)所得In2O3载体中加入去离子水和AgNO3溶液,搅拌1 h,随后加入过量的Na2CO3溶液,80℃水浴3 h,离心,去离子水洗涤,60℃真空干燥,制得以氧化铟为载体负载银的光催化剂。
5.根据权利要求3所述的制备方法,其特征在于:步骤(1)中InCl3的用量为3.6 g,25~28wt%的氨水的用量为18 mL,H2O的用量为18 mL,无水乙醇的用量为108 mL;步骤(2)中AgNO3溶液的浓度为5 mg·mL-1,其加入量为每0.5 g In2O3载体中加入1~5 mL对应1~5 wt%;Na2CO3溶液浓度为1.0 g Na2CO3溶于10 mL去离子水。
6.一种如权利要求1-2任一项所述的以氧化铟为载体负载银的光催化剂的应用,其特征在于:所述的以氧化铟为载体负载银的光催化剂应用于室温及紫外可见光下光催化甲烷无氧偶联的体系。
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