CN109999838B - 一种宽光谱响应硫化钒/凹凸棒石纳米复合材料制备方法及应用 - Google Patents
一种宽光谱响应硫化钒/凹凸棒石纳米复合材料制备方法及应用 Download PDFInfo
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Abstract
本发明属于化工新材料技术领域，涉及一种宽光谱响应硫化钒/凹凸棒石纳米复合材料制备方法及应用。其制备方法为：(1)将Na3VO4·12H2O、CH3CSNH2、凹凸棒石加入去离子水中超声混合均匀。(2)将溶液转移到微波水热釜里进行微波水热反应，(3)将步骤(2)中制备的反应产物用离心机离心，去离子水洗涤并烘干，即得到四硫化钒/凹凸棒石复合光催化材料。本发明运用微波水热法合成四硫化钒/凹凸棒石纳米催化剂，能够在宽光谱(包括紫外到近红外)照射下把N2最大程度的转化成NH3，具有优异的光固氮能力。
Description
技术领域
本发明属于化工新材料领域，特别涉及一种宽光谱响应四硫化钒/凹凸棒石纳米复合材料及其制备方法与光催化固氮应用。
背景技术
氮气占地球大气的主要成分(～78vol％)，但由于N≡N键的裂解具有非常大的活化势垒(941kJ/mol)，因此难以被利用。目前，在工业中广泛实现的人工固氮方法是Haber-Bosch工艺，但是其反应条件需要高温高压，而且污染严重。因此，开发更环保，更低能耗的人工固氮工艺具有重要的社会意义。其中，光催化固氮制氨技术引起了广泛关注。近年来，紫外线(UV)和可见光驱动的光催化剂已被广泛研究，如TiO2，ZnO，WO3，CdS等。然而，紫外线仅占太阳光的5％，可见光占阳光的48％，如何利用到太阳光中约占44％的近红外光(NIR)进行光催化固氮仍是一个挑战。
四硫化钒(VS4)是一种金属硫属元素化合物，由于VS4具有非常窄的带隙(0.8-1.2eV)，吸收范围达到近红外光区域，这使它成为一种有前途的宽光谱光催化剂。比如VS4被用于光催化水分解产氢(Int J Hydrogen Energy,2014,39,16832)，但是，同样因为VS4的带隙过窄，导致了光生电子和空穴对非常容易快速复合，影响了光催化效率。与其它半导体复合构建异质结可显著分离光生载流子，但普遍成本较高，而且往往不能兼顾催化所需的吸附性。作为天然粘土矿物材料，凹凸棒石(ATP)以其成本低廉，大比表面积，优异的吸附性能和独特的多孔结构而广泛用于催化剂载体。另外由于存在氧化铁的组分，ATP也具有一定的半导体特性能有效地构筑异质结分离光生载流子，提高光生载流子的寿命。迄今尚无关于凹凸棒石复合VS4用于宽光谱光催化固氮的报道。
发明内容
其中VS4作为一种窄带隙半导体材料，其光响应范围从紫外光达到近红外光，对太阳光的利用率非常高。然而也由于其窄带隙的特点，光生电子和空穴极易复合，影响了光催化的效率。
为了解决VS4光生电子与空穴极易复合的问题，本发明提供了一种宽光谱响应四硫化钒/凹凸棒石纳米复合光催化材料。利用简易的微波水热法，使VS4晶体在ATP上原位生长，负载粒径均匀的VS4纳米颗粒，构建Z型异质结，促进光生电子与空穴的分离，不仅延长光生电子与空穴的寿命，同时保持光催化剂拥有较高的氧化还原电位，使其能够充分利用太阳光进行光催化固氮反应。
本发明提供的宽光谱响应四硫化钒/凹凸棒石纳米复合光催化材料由VS4纳米微球颗粒与ATP一维纳米棒复合组成，复合材料中，VS4占ATP材料的质量分数为30wt％～70wt％。
本发明还提供了一种宽光谱响应四硫化钒/凹凸棒石纳米复合光催化材料的制备方法：
(1)将一定量的Na3VO4·12H2O、CH3CSNH2、ATP加入到适量去离子水中，超声波分散使其混合均匀，得混合液；其中，Na3VO4在分子水平上被ATP表面的含氧官能团吸附，固定在ATP表面。
(2)将混合液转移到微波水热釜里进行微波水热反应，设定功率400W，设定温度为150～200℃，时间设定为1-5h；
(3)将步骤(2)中制备的产物用离心机离心(10000r/min，2min)分离，收集沉淀物，去离子水清洗3次，烘箱烘干，即得到VS4/ATP复合光催化材料。
本发明还提供了一种上述宽光谱响应四硫化钒/凹凸棒石纳米复合光催化材料的应用，即采用该复合光催化材料进行光催化固氮。
本发明的有益效果在于：
本发明采用了微波水热法进行合成四硫化钒/凹凸棒石复合材料，相比于常规的溶剂热法，微波水热法加热更均匀，更大程度上缩短了反应时间，无需有机溶剂，合成的VS4纳米微球颗粒均匀，粒径更小，催化活性更高。
本发明在复合材料中充分利用了窄带隙半导体光催化材料的特点，光响应范围广(从紫外光拓展到近红外光响应)，光催化反应中充分利用了太阳光。VS4与ATP之间成功地构建了Z型异质结，解决了窄带隙材料光生电子与空穴易复合的缺点，延长了光生载流子的寿命，同时保持了更高的氧化还原电位，大大提高了光催化固氮反应的效率。
附图说明
图1为本发明实施例1制备的60wt％VS4/ATP的扫描显微镜(SEM)图；
图2为本发明实施例1制备的60wt％VS4/ATP的透射电镜(TEM)图。
具体实施方式
实施例1
(1)将0.67g的Na3VO4·12H2O、0.50g的CH3CSNH2、0.5g的ATP加入到适量去离子水中，超声波分散使其混合均匀。Na3VO4在分子水平上被ATP表面的含氧官能团吸附，固定在ATP表面。
(2)将溶液转移到微波水热釜里进行微波水热反应，设定功率400W，设定温度为150℃，时间设定为5h；
(3)将步骤(2)中制备的产物用离心机离心(10000r/min，2min)，去离子水清洗3次，烘箱烘干，即得到60wt％VS4/ATP复合光催化材料。
对所得样品进行扫描电镜SEM(图1)和透射电镜TEM观察(图2)，可以看到在ATP的表面上均匀地复合着VS4纳米微球颗粒。
本发明还提供了一种利用本实施例制备的60wt％VS4/ATP复合光催化材料进行光催化固氮的方法：
将50mg样品分散在50mL Na2SO3水溶液(空穴牺牲剂)的石英反应器中。对样品进行超声处理以形成均匀的悬浮液，然后在黑暗中剧烈搅拌，用纯N2鼓泡，流速为约30mL·min-1，持续30分钟。随后，用300W Xe灯在全光谱下照射悬浮液，功率密度为200mW·cm-2。每隔1h用注射器收集5mL反应溶液，通过离心除去催化剂。使用Nessler试剂法在420nm下利用紫外-可见分光光度计检测产物浓度，再除以催化剂质量和时间，可以得出NH4+产生速率。
在4h光照后，60wt％VS4/ATP达到了铵离子产生速率为247.6μmol·gcat –1·h–1的固氮量。
实施例2
(1)将0.33g的Na3VO4·12H2O、0.25g的CH3CSNH2、0.5g的ATP加入到适量去离子水中，超声波分散使其混合均匀。Na3VO4在分子水平上被ATP表面的含氧官能团吸附，固定在ATP表面。
(2)将溶液转移到微波水热釜里进行微波水热反应，设定功率400W，设定温度为160℃，间设定为4h；
(3)将步骤(2)中制备的产物用离心机离心(10000r/min，2min)，去离子水清洗3次，烘箱烘干，即得到30wt％VS4/ATP复合光催化材料。
后续检测如实施例1。
在4h光照后，30wt％VS4/ATP达到了铵离子产生速率为106.3μmol·gcat –1·h–1的固氮量。
实施例3
(1)将0.45g的Na3VO4·12H2O、0.34g的CH3CSNH2、0.5g的ATP加入到适量去离子水中，超声波分散使其混合均匀。Na3VO4在分子水平上被ATP表面的含氧官能团吸附，固定在ATP表面。
(2)将溶液转移到微波水热釜里进行微波水热反应，设定功率400W，设定温度为170℃时间设定为3h；
(3)将步骤(2)中制备的产物用离心机离心(10000r/min，2min)，去离子水清洗3次，烘箱烘干，即得到40wt％VS4/ATP复合光催化材料。
后续检测如实施例1。
在4h光照后，40wt％VS4/ATP达到了铵离子产生速率为121.7μmol·gcat –1·h–1的固氮量。
实施例4
(1)将0.56g的Na3VO4·12H2O、0.42g的CH3CSNH2、0.5g的ATP加入到适量去离子水中，超声波分散使其混合均匀。Na3VO4在分子水平上被ATP表面的含氧官能团吸附，固定在ATP表面。
(2)将溶液转移到微波水热釜里进行微波水热反应，设定功率400W，设定温度为180℃，间设定为2h；
(3)将步骤(2)中制备的产物用离心机离心(10000r/min，2min)，去离子水清洗3次，烘箱烘干，即得到50wt％VS4/ATP复合光催化材料。
后续检测如实施例1。
在4h光照后，50wt％VS4/ATP达到了铵离子产生速率为166.2μmol·gcat –1·h–1的固氮量。
实施例5
(1)将0.78g的Na3VO4·12H2O、0.59g的CH3CSNH2、0.5g的ATP加入到适量去离子水中，超声波分散使其混合均匀。Na3VO4在分子水平上被ATP表面的含氧官能团吸附，固定在ATP表面。
(2)将溶液转移到微波水热釜里进行微波水热反应，设定功率400W，设定温度为190℃，时间为2h；
(3)将步骤(2)中制备的产物用离心机离心(10000r/min，2min)，去离子水清洗3次，烘箱烘干，即得到70wt％VS4/ATP复合光催化材料。
后续检测如实施例1。
在4h光照后，70wt％VS4/ATP达到了铵离子产生速率为187.1μmol·gcat –1·h–1的固氮量。
对比实施例1
(1)将0.67g的Na3VO4·12H2O、0.50g的CH3CSNH2加入到适量去离子水中，超声波分散使其混合均匀。
(2)将溶液转移到微波水热釜里进行微波水热反应，设定功率400W，设定温度为150℃，时间设定为5h；
(3)将步骤(2)中制备的产物用离心机离心(10000r/min，2min)，去离子水清洗3次，烘箱烘干，即得到VS4光催化材料。
后续检测如实施例1。
在4h光照后，本对比实施例制备的VS4达到的铵离子产生速率仅为17.5μmol·gcat –1·h–1的固氮量。这是由于本对比实施例中只有纯VS4，VS4带隙过窄，光生电子与空穴极易复合，光生载流子寿命太短，因此导致光催化固氮效率比VS4/ATP低。
对比实施例2
(1)将0.67g的Na3VO4·12H2O、0.50g的CH3CSNH2、0.5g的ATP加入到适量乙醇溶液中，超声分散混合均匀。
(2)将溶液转移到高温水热反应釜中里进行溶剂热反应，设定温度为160℃，时间设定为18h，自然冷却至室温；
(3)将步骤(2)中制备的产物用离心机离心(10000r/min，2min)分离，去离子水清洗3次，烘箱烘干，即得到60wt％VS4/ATP复合光催化材料。
后续检测如实施例1。
在4h光照后，本对比实施例制备的VS4/ATP达到铵离子产生速率为33.2μmol·gcat –1·h–1的固氮量。这是由于本对比实施例中使用了传统的溶剂热法合成的VS4/ATP光催化剂，合成过程时间更长，VS4粒径更大，导致VS4纳米颗粒的比表面积变小，催化活性变低。
Claims (1)
1.一种宽光谱响应硫化钒/凹凸棒石纳米复合材料在光催化固氮中的应用，其特征在于：所述复合材料是由VS4纳米微球颗粒与凹凸棒石（ATP）一维纳米棒组成，VS4/ATP复合材料中，VS4占ATP材料的质量分数30wt%~70wt%；
所述宽光谱响应硫化钒/凹凸棒石纳米复合材料制备步骤为：
（1）称取Na3VO4·12H2O、CH3CSNH2、ATP加入到适量去离子水中，超声波分散使其混合均匀，得混合液；
（2）将混合液转移到微波水热釜里进行微波水热反应，反应得产物；微波水热反应设定反应功率为400W，反应温度为150~200℃，反应时间为1-5 h；
（3）将步骤（2）中制备的产物用离心机离心分离，收集沉淀物，去离子水清洗，烘箱烘干，即得到VS4/ATP复合材料。
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