CN112390293B - 超薄二维四氧化三锰和二维Ni-Mn LDH纳米复合材料及其制备方法和应用 - Google Patents
超薄二维四氧化三锰和二维Ni-Mn LDH纳米复合材料及其制备方法和应用 Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 30
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Abstract
本发明公开了一步合成超薄二维(2D)Mn3O4和二维层状双金属氢氧化物(LDH)纳米材料的有序自组装方法,利用水热法一步制备出的2D四氧化三锰(Mn3O4)分散在2D Ni‑Mn LDH上并自组装成微花的纳米复合材料(2D Mn3O4/2D Ni‑Mn LDH),其中2D Mn3O4的厚度在3.75‑4 nm之间,2D Ni‑Mn LDH的厚度约为2 nm;组合后的微花直径约为6 um。本发明制得的2D/2D纳米复合材料可以在光敏剂的条件下,高效选择性光催化二氧化碳还原成一氧化碳。本发明制备工艺简单,周期短,成本低廉,可大规模工业化生产,具有良好的经济效益和环境效益。
Description
技术领域
本发明属于纳米材料制备技术领域,具体涉及一种基于Ni-Mn LDH纳米材料的超薄二维Mn3O4和二维Ni-Mn LDH纳米复合材料及其制备方法和应用。
背景技术
二维(2D)超薄LDH纳米材料由于其具有原子级的厚度(<5 nm)和大的横径比,因此具有高的比表面积、更多暴露的活性位点和高效的电子转移能力,是一种理想的催化材料。由于二维超薄纳米材料具有较高的表面能,因此极易发生团聚和褶皱,引起暴露表面积和活性位点的进一步降低和减少等现象,导致其催化活性的降低和不稳定。目前在二维超薄纳米材料的合成和抑制其团聚的过程,往往需要加入表面活性剂,这会导致表面活性剂吸附在2D材料的表面,进而导致活性位点被包覆,降低了活性位点与反应物之间的有效接触,不利于催化反应的进行。为此,寻找一种无表面活性剂合成2D纳米材料并能够防止其团聚的方法,成为目前的研究热点。
此外,在光催化领域中,光生电子-空穴对的快速复合是制约其工业化应用的主要问题之一。构建2D/2D异质结能够提高可见光的利用率(占太阳光中45%的能量),其形成的内建电场能够有效提高光生载流子的分离效率。2D/2D异质结具有高度耦合和更大的面接触,有利于光生电子-空穴对在界面的快速转移。但是目前2D/2D纳米复合材料是将两种不同的2D纳米材料通过静电自组装或者以表面活性剂为桥连剂直接进行混合,其组装过程不可控,因此制备高度分散的2D/2D纳米复合材料仍存在很多难点。为解决这一难点,设计一种简单的工艺,实现原位同步合成均匀分散的超薄2D/2D纳米材料的制备方法具有重要意义。
发明内容
本发明的目的在于针对现有2D/2D纳米复合材料制备方法、2D纳米片易于团聚、还原活性低的不足,提供了一种工艺简单,制备还原活性高的2D/2D纳米复合材料的绿色合成方法。本发明通过一步水热合成,自组装形成形貌均一、尺寸可控、还原活性高的2D Mn3O4/2D Ni-Mn LDH纳米复合材料,其中2D Mn3O4的厚度在3.75-4 nm之间,2D Ni-Mn LDH的厚度约为2 nm;组合后的微花直径约为6 um。而且所制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料能够高效选择性光催化还原CO2为CO,成本低廉,方法简单,提供了形貌尺寸可控的制备方法,具有良好的经济效益和环境效益,而且还可以进行大规模生产应用。
为实现上述目的,本发明采用如下技术方案:
一步合成超薄二维Mn3O4和二维Ni-Mn LDH纳米材料的有序自组装方法,包括以下原料:甲酸锰(Mn(HCOO)2)、六水合氯化镍(NiCl2·6H2O)、甲醇(CH3OH)。
一步合成超薄二维Mn3O4和二维LDH纳米材料的有序自组装方法:将甲酸锰和六水合氯化镍加入到甲醇中,充分混合溶解,然后将混合溶液转移至聚四氟乙烯衬里的不锈钢高压釜中恒温反应;反应结束后,经冷却、离心分离、洗涤、干燥直至水分完全挥发,获得固态粉末状尺寸均匀高度分散的2D Mn3O4/2D Ni-Mn LDH自组装成微球的纳米复合材料。
所述尺寸均匀高度分散的2D Mn3O4/2D Ni-Mn LDH纳米复合材料的制备方法具体包括以下步骤:
(1)将二价锰盐和二价镍盐加入到醇中,充分混合溶解,制成均匀分散的反应前驱液;
(2)然后将反应前驱液转移至聚四氟乙烯衬里的不锈钢高压釜中恒温反应;
(3)反应结束后,经冷却、离心分离、洗涤、干燥直至水分完全挥发,获得固态粉末状2D Mn3O4/2D Ni-Mn LDH纳米复合材料。
进一步地,步骤(1)所述的二价锰盐为甲酸锰Mn(HCOO)2;所述的二价镍盐为六水合氯化镍NiCl2·6H2O;醇为甲醇CH3OH。
进一步地,步骤(1)中二价锰盐与二价镍盐的摩尔比为20:3 – 5:2,醇的用量为60mL,此反应为一个相变过程,在锰镍摩尔比为20:3~5:2的范围内其是一个混合物相。在反应初期,先生成Mn3O4,随着反应的进行,Mn3O4将会转化为Mn-LDH,但当镍含量太低时,其不会向Mn-LDH转化,而当镍含量太高时,会导致其完全转化为Ni-Mn LDH,而非形成2D/2D的复合结构。
进一步地,步骤(1)所述的混合溶解具体为:磁力搅拌;搅拌速度为300-800rpm;搅拌时间为15 - 30min。
进一步地,步骤(2)所述的恒温反应具体为:在180 ℃恒温反应4 - 36 h。
进一步地,步骤(3)所述的冷却具体为:自然冷却到室温。
进一步地,步骤(3)所述的洗涤具体为:用去离子水和乙醇分别洗涤3次。
进一步地,步骤(3)所述的干燥具体为:干燥方式为真空-53℃冷冻干燥;干燥时间为8 - 12 h
其中长约70 - 150 nm、宽约30 - 60 nm、厚度约3.75 - 4.0 nm的2D Mn3O4,均匀分散在厚度约为2 nm,边长为 4 - 8 um的2D Ni-Mn LDH纳米片上,如图1所示。
本发明的有益效果在于:
(1)本发明采用一步水热合成法,实现原位同步制备了均匀高度分散的2D Mn3O4/2D Ni-Mn LDH纳米复合材料,提供了一种新的关于二维-二维纳米材料复合的方法,为2D/2D超薄纳米片的复合组装提供了新思路。
(2)本发明制备的2D Mn3O4/2D Ni-Mn LDH纳米复合材料能够形成自支撑结构的花状微球,能够有效的避免纳米片的团聚和表面活性剂的使用。
(3)本发明制备的2D Mn3O4/2D Ni-Mn LDH纳米复合材料,2D Mn3O4和2D Ni-MnLDH之间能够高效协同,显著抑制光生电子-空穴对的复合,促进电子的转移,实现高效选择性光催化还原二氧化碳。
(4)本发明的制备方法所需要原材料和设备简单易取,流程工艺简单、易操作和安全,成本相对低廉,可大规模工业化生产;与其他过渡金属元素相比对环境污染小,具有高的选择性和效率,是一种生态环境友好型材料,具有很好的推广应用价值。
附图说明
图1是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料的扫描电子显微镜(SEM)图;
图2是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料的透射电子显微镜(TEM)图;
图3是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料、对比例1制得的OVs-Mn3O4和比例2制得的/Ni-Mn LDH纳米片的X射线衍射(XRD)图;
图4是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料的原子力显微镜(AFM)图;
图5是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料、对比例1制得的OVs-Mn3O4、对比例2制得的Ni-Mn LDH纳米片和市售Mn3O4的N2吸附-脱附等温线(BET)图;
图6是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料、对比例1制得的OVs-Mn3O4、对比例2制得的Ni-Mn LDH纳米片和市售Mn3O4的荧光吸收谱图;
图7是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料进行循环反应时,一氧化碳产量示意图;
图8是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料、对比例1制得的OVs-Mn3O4、对比例2制得的Ni-Mn LDH纳米片和市售Mn3O4,一氧化碳产量随反应时间变化示意图;
图9是本发明实施例1,锰镍摩尔比为10 : 3,增加恒温反应时间至4 h制得的2DMn3O4/2D Ni-Mn LDH纳米复合材料的SEM图;
图10是本发明实施例1,锰镍摩尔比为10 : 3,增加恒温反应时间至6 h制得的2DMn3O4/2D Ni-Mn LDH纳米复合材料的SEM图;
图11是本发明实施例1,锰镍摩尔比为10 : 3,增加恒温反应时间至36 h制得的2DMn3O4/2D Ni-Mn LDH纳米复合材料的SEM图;
图12是本发明实施例1,改变锰镍摩尔比至20: 3制得的2D Mn3O4/2D Ni-Mn LDH纳米复合的SEM图;
图13是本发明实施例1,改变锰镍摩尔比至20:3制得的2D Mn3O4/2D Ni-Mn LDH纳米复合的TEM图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图即实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用于解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以结合。
实施例1
Mn3O4/Ni-Mn LDH纳米复合材料的制备:
(1)用电子天平称取1 mmol甲酸锰Mn(HCOO)2和0.3 mmol六水合氯化镍NiCl2·6H2O,用量筒量取60ml甲醇,将三者混合;
(2)然后将混合液转移至聚四氟乙烯衬里的不锈钢高压釜中,并在180 ℃下恒温反应18 h,反应结束后自然冷却至室温;
(3)用离心机离心分离样品得到固态粉末,转速为6000 rpm;并用乙醇和去离子水分别洗涤三次;
(4)通过冷冻干燥过夜至水分完全挥发,获得2D Mn3O4/2D Ni-Mn LDH纳米复合材料。图2可以看出,叶子形状的是2D Mn3O4,花状微球的骨架是2D Ni-Mn LDH纳米片,2DMn3O4尺寸均匀且高度分散在2D Ni-Mn LDH纳米片上。从图4也可以看出,2D Mn3O4分布在2DNi-Mn LDH纳米片上,且2D Mn3O4的厚度为3.75nm。
对比例1
OVs-Mn3O4的制备:
(1)用电子天平称取1 mmol甲酸锰Mn(HCOO)2,用量筒量取60 ml甲醇,将二者混合;
(2)然后将混合液转移至聚四氟乙烯衬里的不锈钢高压釜中,并在180 ℃下恒温反应18 h,反应结束后自然冷却至室温;
(3)用离心机离心分离样品得到固态粉末,转速为6000 rpm;并用乙醇和去离子水分别洗涤三次;
(4)通过冷冻干燥过夜至水分完全挥发,获得OVs-Mn3O4纳米材料。
对比例2
Ni-Mn LDH纳米片的制备
(1)然后用电子天平称取1 mmol甲酸锰Mn(HCOO)2和0.7 mmol六水合氯化镍NiCl2·6H2O,用量筒量取60 ml甲醇,将三者混合;
(2)然后将混合液转移至聚四氟乙烯衬里的不锈钢高压釜中,并在180 ℃下恒温反应18 h,反应结束后自然冷却至室温;
(3)用离心机离心分离样品得到固态粉末,转速为6000 rpm;并用乙醇、去离子水洗涤三次;
(4)通过冷冻干燥过夜至水分完全挥发,获得Ni-Mn LDH纳米复合材料。
可见光照射下二氧化碳还原实验测试:
应用实施例1
将实施例1中得到的2D Mn3O4/2D Ni-Mn LDH纳米复合材料用于二氧化碳还原,具体步骤如下:
(1)取4.5 mg的2D Mn3O4/2D Ni-Mn LDH催化剂、8.5 mg六水合三联吡啶氯化钌加入到含有1 mL去离子水、3 mL 乙腈、1 mL三乙醇胺混合液的石英反应器中;
(2)将整个石英反应器进行脱气;
(3)用纯的二氧化碳对石英反应器重复充气3次;
(4)在25 ℃下,将石英反应器置于300 W的氙灯下照射;
(5)在一定时间后,取0.5 mL产生的气体,做气相色谱。
应用实施例2
将对比例1中得到的OVs-Mn3O4用于二氧化碳还原,具体步骤如下:
(1)取4.5 mg的OVs-Mn3O4催化剂、8.5 mg六水合三联吡啶氯化钌加入到含有1 mL去离子水、3 mL乙腈、1 mL三乙醇胺混合液的石英反应器中;
(2)将整个石英反应器进行脱气;
(3)用纯的二氧化碳对石英反应器重复充气3次;
(4)在25 ℃下,将石英反应器置于300 W的氙灯下照射;
(5)在一定时间后,取0.5 mL产生的气体,做气相色谱。
应用实施例3
将对比例2中得到的Ni-Mn LDH纳米片用于二氧化碳还原,具体步骤如下:
(1)取4.5 mg的Ni-Mn LDH催化剂、8.5 mg六水合三联吡啶氯化钌加入到含有1 mL去离子水、3 mL乙腈、1 mL三乙醇胺混合液的石英反应器中;
(2)将整个石英反应器进行脱气;
(3)用纯的二氧化碳对石英反应器重复充气3次;
(4)在25 ℃下,将石英反应器置于300 W的氙灯下照射;
(5)在一定时间后,取0.5 mL产生的气体,做气相色谱。
图5是本发明实施例1制得的2D Mn3O4/2D Ni-Mn LDH纳米复合材料、对比例1制得的OVs-Mn3O4、对比例2制得的Ni-Mn LDH纳米片和市售Mn3O4的BET图,可以看出2D Mn3O4/2DNi-Mn LDH纳米复合材料具有较大的比表面积,有利于其催化性能。市售Mn3O4对于催化二氧化碳还原不具备活性。OVs-Mn3O4对于催化二氧化碳还原有一定的活性,CO释放速率为1950μmol·g-1·h-1;但选择性较低,为43.80%。 Ni-Mn LDH纳米片对于催化二氧化碳还原有一定的活性,一氧化碳释放速率为1436 umol·g-1·h-1;但选择性较高,为98.94%。 而Mn3O4/Ni-Mn LDH的2D / 2D组装结构纳米片对于催化二氧化碳还原有较高的活性,其一氧化碳释放速率为3577 μmol·g-1·h-1,是OVs- Mn3O4释放CO速率的207%,是Ni-Mn LDH纳米片释放一氧化碳速率的249%。此外,它的选择性高达94.8%,接近Ni-Mn LDH纳米片的高选择性(98.94%)。从图7中可以看出本发明制备得到的2D Mn3O4/2D Ni-Mn LDH纳米复合材料具有优异的循环性能,在循环4次后依然保持优异的对二氧化碳催化还原性能。从图8中可以看出随着反应时间的增加,本发明制备得到的2D Mn3O4/2D Ni-Mn LDH纳米复合材料的CO的产率逐渐增加且增加明显,而其他三种材料的CO的产率虽然也稍有增加,但增加不明显,而且产率也一直低于本发明制备得到的2D Mn3O4/2D Ni-Mn LDH纳米复合材料。从图1、9、10、11中可以看出,在锰镍摩尔比为10:3时,在本发明限定的时间范围内均可以得到2D Mn3O4/2DNi-Mn LDH纳米复合材料。从图1、12中可以看出,在反应时间为18h时,在本发明限定的锰镍摩尔比范围内均可以得到2D Mn3O4/2D Ni-Mn LDH纳米复合材料。以上两点也说明了,在本发明限定的时间和锰镍摩尔比范围内,均可以得到2D Mn3O4/2D Ni-Mn LDH纳米复合材料。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进,均应包含在本发明的保护范围之内。
Claims (6)
1.一种超薄二维Mn3O4和二维Ni-Mn LDH纳米复合材料的制备方法,其特征在于:包括以下步骤:
(1)将二价锰盐和二价镍盐加入到醇中,充分混合溶解,制成均匀分散的反应前驱液;
(2)然后将反应前驱液转移至聚四氟乙烯衬里的不锈钢高压釜中恒温反应;
(3)反应结束后,经冷却、离心、洗涤、干燥直至水分完全挥发,获得固态粉末状2DMn3O4/2D Ni-Mn LDH纳米复合材料;
步骤(1)所述的锰盐为甲酸锰Mn(HCOO)2;二价镍盐为六水合氯化镍NiCl2·6H2O;醇为甲醇;步骤(1)中二价锰盐、二价镍盐的摩尔比为20:3 ~ 5:2,醇用量为60 mL,步骤(2)所述的恒温反应具体为:在180 ℃恒温反应4-36 h。
2.根据权利要求1所述的制备方法,其特征在于:超薄二维Mn3O4的厚度在3.75-4 nm之间;二维LDH纳米材料厚度小于5nm。
3.根据权利要求1所述的制备方法,其特征在于:步骤(1)所述的混合溶解具体为:在转速300-800rpm条件下,搅拌15-30min。
4.根据权利要求1所述的制备方法,其特征在于:步骤(3)所述的离心和洗涤具体为:在转速6000 rpm的离心机下离心,用乙醇和去离子水分别洗涤3次。
5.根据权利要求1所述的制备方法,其特征在于:步骤(3)所述的干燥具体为:干燥方式为真空-53℃冷冻干燥,干燥时间为8-12 h。
6.一种如权利要求1-5任一项所述制备方法制得的超薄二维Mn3O4和二维Ni-Mn LDH纳米复合材料在高效催化二氧化碳还原中的应用。
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