CN110624534A - 一种生物遗态的wo3光催化剂及其制备方法和应用 - Google Patents
一种生物遗态的wo3光催化剂及其制备方法和应用 Download PDFInfo
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- CN110624534A CN110624534A CN201910997511.8A CN201910997511A CN110624534A CN 110624534 A CN110624534 A CN 110624534A CN 201910997511 A CN201910997511 A CN 201910997511A CN 110624534 A CN110624534 A CN 110624534A
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- photocatalyst
- tungsten source
- biological
- rice hulls
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- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 37
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010937 tungsten Substances 0.000 claims abstract description 36
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- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000011343 solid material Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
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- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 49
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- 229940039790 sodium oxalate Drugs 0.000 description 3
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
本发明提供了一种生物遗态的WO3光催化剂及其制备方法和应用,属于光催化技术领域。本发明的制备方法,包括以下步骤:将稻壳浸渍到钨源溶液中,固液分离后对所得固体物料进行焙烧,得到生物遗态的WO3光催化剂。本发明利用稻壳为生物模板剂,稻壳含有大量的二氧化硅,具有硅‑碳网状结构,将稻壳浸渍到钨源溶液中,经焙烧后,钨源复制了稻壳的硅‑碳网状结构,形成包括微孔和介孔的分级结构,具有良好的吸附性,同时,焙烧过程中稻壳的碳掺杂到WO3晶格中,利于WO3晶格电荷之间的转移,降低了WO3的禁带宽度,提高了WO3的光催化反应性能。
Description
技术领域
本发明涉及光催化技术领域,尤其涉及一种生物遗态的WO3光催化剂及其制备方法和应用。
背景技术
生物仿生材料因其结构独特、原料广泛、成本低廉、制备方法简单等优越性成为科学研究热点,利用生物启发或模仿仿生生物的各种功能、结构、成分来设计开发具有微米或纳米分级结构并且继承原来生物体特有形貌结构的材料,可应用于环境、光学、能源等领域。生物仿生材料所用模板几乎包括整个生态***,如植物、动物、微生物等。
高雪等人以油菜花粉为生物模板,硝酸锌为锌源制备了一种六方纤锌矿结构的纳米氧化锌(高雪,刘宇彤,王煜等.生物模板法制备纳米氧化锌[J].化学通报,2019,82(1)63:67.);廉畅等人以壳聚糖为生物模板制备了介孔纳米氧化铈(廉畅,李长波,赵国峥等.生物模板法合成多孔结构氧化铈及其吸附性能研究[J].化工新型材料,2018,46(9):202-204.);Robert等人以软木粉末为生物模板制备了软磁性生态陶瓷(Pullar R C,MarquesP,Amaral J,et al.Magnetic wood-based biomorphic Sr3Co2Fe24O41Z-typehexaferrite ecoceramics made from cork templates[J].Materials&Design,2015,82:297-303.);李林璇等人以改性秸秆为生物模板制备出改性秸秆-Fe3O4复合材料(李林璇,廖云开,范世锁.改性秸秆-Fe3O4复合材料对染料废水中亚甲基蓝的去除研究[J].农业环境科学学报,2019,38(5):1130-1141.)。然而以生物模板制备WO3光催化剂的研究却鲜有报道。
发明内容
本发明的目的在于提供一种生物遗态的WO3光催化剂及其制备方法和应用,本发明制备的WO3光催化剂具有分级多孔结构,应用于亚甲蓝废水的处理,具有良好的处理效果。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种生物遗态的WO3光催化剂的制备方法,包括以下步骤:将稻壳浸渍到钨源溶液中,固液分离后对所得固体物料进行焙烧,得到生物遗态的WO3光催化剂。
优选的,所述浸渍前,还包括对稻壳依次进行清洗、酸浸和氨水抽提。
优选的,所述酸浸采用的酸液为盐酸,所述盐酸的质量浓度为5~7%;酸浸的时间为3~5h。
优选的,进行氨水抽提时所用氨水的质量浓度为5~7%,抽提时间为3~4h。
优选的,所述钨源溶液的钨源为钨酸钙或氯化钨;所述钨源溶液的溶剂为乙醇或甲醇;所述钨源溶液中钨源和溶剂的比例为(0.1~5)g:40mL。
优选的,所述浸渍的时间为46~50h。
优选的,所述焙烧的温度为540~550℃,保温时间为4~6h;所述焙烧的氛围为空气氛围。
优选的,自室温升至所述焙烧的温度,升温速率为1.5~2℃/min。
本发明提供了上述方案所述制备方法制备得到的生物遗态的WO3光催化剂。
本发明提供了上述方案所述生物遗态的WO3光催化剂在处理亚甲基蓝废水中的应用。
本发明提供了一种生物遗态的WO3光催化剂的制备方法,包括以下步骤:将稻壳浸渍到钨源溶液中,固液分离后对所得固体物料进行焙烧,得到生物遗态的WO3光催化剂。本发明利用稻壳为生物模板剂,稻壳含有大量的二氧化硅,具有硅-碳网状结构,将稻壳浸渍到钨源溶液中,经焙烧后,钨源复制了稻壳的硅-碳网状结构,形成包括微孔和介孔的分级结构,具有良好的吸附性,同时,焙烧过程中稻壳的碳掺杂到WO3晶格中,利于WO3晶格电荷之间的转移,降低了WO3的禁带宽度,提高了WO3的光催化反应性能。实施例结果表明,将本发明制备的生物遗态的WO3光催化剂用于处理亚甲基蓝废水,对亚甲基蓝的降解率要明显高于市售的WO3,表明本发明制备的生物遗态的WO3光催化剂具有良好的光催化性能。
附图说明
图1为B-WO3和E-WO3的XRD图谱;
图2为B-WO3和E-WO3的SEM照片;
图3为B-WO3的TEM照片;
图4为B-WO3的XPS测试分析结果图;
图5为B-WO3的N2吸附-脱附等温线及BJH孔径分布曲线;
图6为B-WO3和E-WO3的紫外-可见漫反射光谱;
图7为钨源溶液浓度对降解率的影响图;
图8为B-WO3和E-WO3在不同条件下对亚甲基蓝溶液的降解情况图;
图9为亚甲基蓝初始浓度对降解率的影响图;
图10为WO3投加量对降解率的影响图;
图11为B-WO3降解亚甲基蓝的紫外-可见吸收光谱;
图12为B-WO3降解亚甲基蓝溶液时,总有机碳浓度(TOC)随反应时间变化图;
图13为活性物种捕捉实验结果图。
具体实施方式
本发明提供了一种生物遗态的WO3光催化剂的制备方法,包括以下步骤:将稻壳浸渍到钨源溶液中,固液分离后对所得固体物料进行焙烧,得到生物遗态的WO3光催化剂。
在本发明中,未经特殊说明,所用原料均为本领域熟知的市售商品。
本发明将稻壳浸渍到钨源溶液中。在本发明中,所述稻壳优选为当季的稻壳。所述钨源溶液的钨源优选为钨酸钙或氯化钨,更优选为氯化钨;所述钨源溶液的溶剂优选为乙醇或甲醇;所述钨源溶液中钨源和溶剂的比例优选为(0.1~5)g:40mL,更优选为(0.5~1)g:40mL,最优选为0.793g:40mL。在本发明中,所述稻壳与钨源溶液的用量比优选为50g:40mL。
所述浸渍前,本发明优选还包括对稻壳依次进行清洗、酸浸和氨水抽提。在本发明中,所述清洗用洗液优选为水,本发明优选清洗3次以清除稻壳表面杂质。在本发明中,所述酸浸采用的酸液优选为盐酸,所述盐酸的质量浓度优选为5~7%,更优选为5%;所述酸浸的时间优选为3~5h。本发明对所述酸浸时盐酸的用量没有特殊要求,能够将稻壳完全浸没即可。本发明利用酸浸去除稻壳中的钙离子。完成酸浸后,本发明优选采用水将酸浸后稻壳清洗至中性。在本发明中,进行氨水抽提时所用氨水的质量浓度优选为5~7%,更优选为5%;抽提时间优选为3~4h。本发明对所述氨水的用量没有特殊要求,能够将稻壳完全浸没即可。本发明利用氨水进行抽提,有利于增加稻壳的吸附性。完成氨水抽提后,本发明优选还包括对抽提后的稻壳清洗至中性以及烘干。在本发明中,所述烘干的温度优选为60~80℃。本发明对所述烘干的时间没有特殊要求,以稻壳完全干燥为宜。
在本发明中,所述浸渍的时间优选为46~50h。本发明所述浸渍过程中,钨源溶液将稻壳包裹并进入稻壳的多孔结构。
完成所述浸渍后,本发明对所得体系进行固液分离,得到固体物料。本发明对所述固液分离的方式没有特殊要求,本领域熟知的固液分离方式均可。在本发明的实施例中,具体是将多余的液体倒掉,仅留下固体物料。
得到固体物料后,本发明对所述固体物料进行焙烧,得到生物遗态的WO3光催化剂。
焙烧前,本发明优选还包括对所述固体物料依次进行清洗和烘干。本发明优选采用蒸馏水进行所述清洗。在本发明中,所述烘干的温度优选为60~80℃,更优选为60℃。本发明对所述烘干的时间没有特殊要求,以稻壳完全干燥为宜。
在本发明中,所述焙烧的温度优选为540~550℃,保温时间优选为4~6h;所述焙烧的氛围优选为空气氛围。本发明优选自室温升至所述焙烧的温度,升温速率优选为1.5~2℃/min。本发明所述焙烧过程中,稻壳的多孔遗态结构被打开,钨源复制稻壳的多孔结构,同时钨源与稻壳中的碳和空气中的氧气反应,生成生物遗态的WO3,在此过程中,稻壳中的碳不可避免的掺入到WO3的晶格中,利于WO3晶格电荷之间的转移,同时降低了WO3的禁带宽度,提高了WO3的光催化反应性能。
焙烧之后,本发明优选还包括对焙烧后的产物进行研磨,得到的生物遗态的WO3光催化剂。本发明对所述研磨的具体实施方式没有特殊要求,采用本领域熟知的研磨方式即可。
本发明提供了上述方案所述制备方法制备得到的生物遗态的WO3光催化剂。本发明的生物遗态的WO3光催化剂复制了稻壳的硅-碳网状结构,具有大量的微孔和介孔,呈明显的分级结构,较市售的WO3具有更大的比表面积和更好的吸附性能,比表面积高达199.18m2/g,平均孔径为5~6nm,孔径主要分布在2~12nm之间。在本发明中,所述生物遗态的WO3光催化剂优选为纳米颗粒,粒径优选为40~50nm。本发明的生物遗态的WO3光催化剂不可避免的掺杂有少量的碳,碳的掺入有利于WO3晶格电荷之间的转移,同时降低了WO3的禁带宽度,提高了WO3的光催化反应性能。
本发明提供了上述方案所述生物遗态的WO3光催化剂在处理亚甲基蓝废水中的应用。本发明对所述应用的方式没有特殊要求,选用本领域熟知的应用方式即可。在本发明中,所述亚甲基蓝废水中亚甲基蓝的浓度优选为5~30mg/L,更优选为10mg/L。在本发明中,所述生物遗态的WO3光催化剂的投加量优选为500~600mg/L。本发明优选在光照和搅拌条件下对亚甲基蓝废水进行处理。在本发明中,所述光照优选为自然光照,在本发明的实施例中,具体是采用300W的氙灯来模拟自然太阳光。本发明对所述搅拌的速率没有特殊要求,采用本领域熟知的搅拌速率即可。在本发明中,所述处理的时间优选为3~4h。
下面结合实施例对本发明提供的生物遗态的WO3光催化剂及其制备方法和应用进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
稻壳预处理:取一定量的稻壳,用清水清洗3次以去除表面杂质,用质量浓度5%的盐酸浸渍3h,用蒸馏水洗至中性。将水洗后的稻壳放入质量浓度5%的稀氨水抽提3h,倒掉多余液体,然后用蒸馏水洗至中性,置于60℃烘箱内烘干;
稻壳浸渍:分别取0.158g、0.793g、1.58g和4.76gWCl6溶于40mL乙醇溶剂中,形成均匀深蓝色钨盐溶液,将烘干好的稻壳50g完全浸渍到钨盐溶液中48h,浸渍完成后用蒸馏水清洗至稻壳表面至无色,置于60℃烘箱内烘干;
稻壳焙烧:将烘干好的稻壳放入马弗炉中,升温速度为2℃/min,在550℃、空气氛围下焙烧4h,研磨,制备出生物遗态的WO3样品。将四种WO3样品分别标记为A-WO3、B-WO3、C-WO3和D-WO3。
将市售粉末的WO3标记为E-WO3。
结构表征
图1为B-WO3和E-WO3的XRD图谱。由图1可知,B-WO3和E-WO3在2θ=23.05°、24.21°、28.76°、33.79°、41.67°、50.54°和54.22°处特征衍射峰分别可以对应(002)、(020)、(112)、(022)、(222)、(114)和(124),与JCPDS No.72-1465的WO3基本一致。此外,B-WO3比E-WO3具有较好的衍射峰,衍射线比较强,衍射峰的半高宽接近仪器测量的宽度,说明B-WO3结晶性良好,尺寸较小。根据Scherrer公式(式中D代表晶粒直径,K为常数0.89;λ为X射线的特征波长;θ为衍射角;β(θ)为衍射峰的半高峰宽),计算B-WO3平均晶粒尺寸为48nm,E-WO3平均晶粒尺寸为93nm,说明稻壳有效抑制了晶粒生长。
图2为B-WO3和E-WO3的SEM照片。通过SEM可以直接观察B-WO3和E-WO3的形貌,图像具有较强的立体感。图2中(A)和(B)是不同放大倍率下B-WO3的SEM照片,图2中(C)和(D)是不同放大倍率下E-WO3的SEM照片。由图2中(A)可以看到B-WO3形貌为球形结构;(B)可以更清楚看到WO3的形貌,WO3表面结构呈多孔,有效复制了稻壳本身的生物结构,并且有规则地在模板(即稻壳)表面上生长,颗粒尺寸均在40~50nm左右,与XRD晶粒尺寸基本一致,属于纳米级颗粒。图2中(C)和(D)可以清楚看到E-WO3呈棒状结构,不具有分级多孔结构。
图3为B-WO3的TEM照片。TEM不仅可以观察B-WO3的形貌,还可以深入观察内部,其分辨率高于SEM。由图3的(A)可知,B-WO3是由多个WO3晶粒不同晶面生长组成,形成的表面较为紧密,粒子较为完整,(B)可以清楚看到每个晶粒之间紧密连接,比表面积较大,(C)显示了B-WO3晶格条纹,其晶格条纹均匀分布,通过与JCPDS标准卡的数据比较,三组晶格条纹间距为2.63nm、3.03nm、3.78nm,对应其(220)、(211)、(020)面,说明了B-WO3粗糙表面是由均匀分散的三氧化钨纳米颗粒组成,同时也说明B-WO3均匀复制硅-碳网状结构,可以进一步抑制三氧化钨的聚集。
为了研究B-WO3的元素组成及表面化学态,对其进行了XPS测试分析,结果如图4所示。图4中(A)是B-WO3的XPS全谱图,证实了其元素主要由W、O、C、Si组成。图4中,(B)是O1s的XPS谱图,通过使用Xpseak4.1程序中的Lorentzian-Gaussian对去除背景的O1s分峰拟合,O1s谱图可以分为532.7、536.7eV两个峰,在532.7eV结合能处峰与B-WO3表面上吸附的氧化物有关,在536.7eV结合能处峰属于B-WO3表面的羟基氧,从而提高光催化性能。图4中,(C)是主要元素W4f的高分辨XPS图谱,可以看出图中有两个峰出现,其位置分别在结合能为35.6eV和37.7eV处,为W4f(W4f5/2和W4f7/2)自旋-轨道能量***所产生,W4f5/2和W4f7/2的电子结合能差为2.1eV,表明W以正六价态存在。图4中,(D)是主要元素C1s的高分辨XPS图谱,其有两种峰的键能组成,分别为284.8eV和288.1eV,主峰284.8eV通常被认为基准峰进行校准的碳源污染或者空气污染引起,次峰288.1eV主要是构成C=O化学键,这归因于稻壳中少量的碳元素掺杂到B-WO3晶格中,利于B-WO3晶格电荷之间转移。
光催化材料吸附比表面积大小及孔径大小是决定光催化活性的一个重要因素,所以对B-WO3进行了氮气等温吸附曲线测试(E-WO3不具备分级多孔结构,仅对B-WO3做其表征)。图5为B-WO3的N2吸附-脱附等温线及BJH孔径分布曲线,其中,(A)是B-WO3的N2吸附-脱附等温线,(B)是B-WO3的BJH孔径分布曲线,参考国际纯粹和应用化学联合会(IUPAC)的分类,可以看出吸附曲线属于IV类型H3型滞后环,这表明了有微孔和介孔存在,并且根据BJH孔径分布曲线也能看出微孔占的比例较大,说明WO3具有丰富的孔结构,较好地保留了稻壳的分级多孔结构,也证实了该材料具有很好的吸附性作用。B-WO3的BET比表面积为199.18m2/g,平均孔径大小为5.95nm,主要分布在2~12nm之间。
为了对比B-WO3和E-WO3的光学性能,B-WO3和E-WO3的紫外-可见漫反射光谱(波长范围为200~700nm)如图6所示。图6显示,E-WO3在紫外区域有很好的吸收,并在可见区域也有很好的吸收,吸收边缘为473nm左右,表现出E-WO3具有吸收可见光的能力。而B-WO3显示的吸收边缘为508nm左右,大于E-WO3。由于尺寸差异,B-WO3相比于E-WO3吸收范围发生红移,意味着更多的可见光可被生物遗态的WO3所吸收并且激发催化剂产生更多的电子空穴对。根据公式Eg(eV)=hc/λ(式中:Eg(eV)是带隙能量;h是普朗克常数;c是光速;λ是吸收波长)计算禁带宽度,可以计算出B-WO3为2.44eV,E-WO3的禁带宽度为2.62eV,可以发现B-WO3小于E-WO3的禁带宽度,这样电子跃迁所需要能量较少,有利于进行光催化反应。
应用例
将市售的E-WO3与制备的A-WO3、B-WO3、C-WO3、D-WO3样品置于不同的初始浓度,体积100mL的亚甲基蓝溶液进行降解试验,并计算降解率。在光照前暗吸附30min,使得催化剂-染料达到吸附脱附平衡,用300W氙灯为光源模拟自然太阳光。实验过程中不断搅拌,每间隔30min取2mL,过0.22μm有机滤膜后经紫外-可见分光光度计在665nm处测定其吸光度。计算亚甲基蓝的降解率=(1-C/C0)×100%,其中:C0为亚甲基蓝催化前的吸光度,C为亚甲基蓝某个时刻吸光度。
1.钨源溶液浓度对降解率的影响
按照应用例的步骤,将实施例1制备的A-WO3、B-WO3、C-WO3、D-WO3样品分别置于100mL浓度为10mg/L的亚甲基蓝溶液进行降解试验,结果如图7所示。图7显示,光照3.5h后,A-WO3、B-WO3、C-WO3、D-WO3对亚甲基蓝均具有较好的降解效果;同时还发现,随钨源溶液浓度的增加,制得的催化剂对亚甲基蓝的降解率先增大后减小,说明钨源溶液浓度对光催化剂的催化性能有重要影响,这可能是由于钨源溶液浓度不同,导致最终得到的光催化剂的表面积和粒径不同导致的,由图7可知,当稻壳用量为50g时,钨源溶液的浓度为0.793g/40mL,制得的光催化剂对亚甲基蓝的降解效果最好(即B-WO3)。
2.光催化对比试验
向三份初始浓度为10mg/L、体积100mL的亚甲基蓝溶液中分别投加光催化剂,其中两份各投加50mg B-WO3,第三份投加50mg E-WO3,在不同条件下的降解情况如图8所示,图8中,B-WO3+Sunlight代表投加B-WO3后,先暗吸附30min,然后光照3.5h;E-WO3+Sunlight代表投加E-WO3后,先暗吸附30min,然后光照3.5h;B-WO3代表投加B-WO3暗吸附30min后,继续在黑暗条件下处理3.5h。图8显示,投加E-WO3暗吸附30min仅降解了12%,这是由于市售粉末WO3不具有分级多孔结构,导致吸附性较差。而B-WO3暗吸附30min溶液浓度降低了近60%左右,继续在无光照条件下处理3.5h溶液浓度降低了约69%,说明B-WO3比表面积较大,与BET表征的结果相一致。投加B-WO3先暗吸附30min,后光照3.5h对亚甲基蓝的降解率达到96%左右,表明以稻壳为模板的分级多孔结构具有一定强吸附作用,在氙灯照射下,B-WO3展现出较强的光催化活性,能够有效降解亚甲基蓝溶液。
3.亚甲基蓝(MB)初始浓度对降解率的影响
为了研究MB初始浓度对降解率的影响,MB选取5mg/L、10mg/L、20mg/L、30mg/L四个初始浓度,光催化剂选用B-WO3,投加量为50mg,其他参数和步骤同应用例,降解结果如图9所示。由图9可知,当其他条件不变时,随着初始浓度的增加,MB的降解率分别为93%、96%、88%、85%。说明MB初始浓度为5mg/L时,染料吸附在光催化剂表面的活性位点没有达到动态平衡,初始浓度增加到10mg/L时,活性位点达到动态平衡点,继续增加时,染料分子吸附在光催化剂表面的活性位点增多,使得吸附在光催化剂表面的羟基自由基和超氧自由基位点减少,从而导致降解率降低。
4.WO3投加量对降解率的影响
MB的初始浓度为10mg/L,投加的光催化剂为B-WO3,其他条件同应用例,研究WO3的投加量对MB降解效果的影响。不同B-WO3的投加量对MB降解率结果如图10所示。从图10可以看出,随着光催化剂投加量的增加,光催化剂提供的活性中心增加,增大吸附性,当光催化剂对染料的吸附达到动态平衡后,过多的催化剂会影响光能吸收,从而影响羟基自由基和超氧自由基、空穴-电子对的数量,影响光催化效果。
5.光催化性能机理
图11是B-WO3降解亚甲基蓝的紫外-可见吸收光谱(投加量为50mg,亚甲基蓝浓度为10mg/L,其他同应用例)。随着氙灯照射时间增加,亚甲基蓝的吸光度逐渐减小,其浓度降低,3.5h后溶液几乎无色,降解率为96%,说明在短时间内B-WO3光催化降解MB效率高。
B-WO3降解亚甲基蓝溶液时,总有机碳浓度(TOC)随反应时间变化而变化,结果如图12所示。图12显示,当随着反应持续进行,TOC浓度逐渐减小,光照3.5h后,TOC的去除率为86%,然而亚甲基蓝降解率为96%,说明这个过程不是简单的脱色反应,而是一个深度氧化矿化的过程。
综上可知,亚甲基蓝溶液初始浓度为10mg/L,B-WO3催化剂投加量为50mg,脱色效率最好,故选择B-WO3在氙灯下光催化降解100mL、初始浓度10mg/L的亚甲基蓝溶液进行活性物种捕获,分别向溶液加入1mmol的草酸钠、异丙醇、硫代硫酸钠和对苯醌,草酸钠为空穴(h+)捕获剂,异丙醇为羟基自由基(·OH)捕获剂,硫代硫酸钠为电子(e-)捕获剂,对苯醌为超氧自由基(·O2 -)捕获剂。通过对比降解实验结果,判断B-WO3降解MB的主要活性物种。从图13中可知,B-WO3光降解MB过程中,对苯醌和硫代硫酸钠具有强的抑制作用,草酸钠和异丙醇抑制不明显,这表明·O2-是主要的活性物质。
根据捕捉实验的结果,可以推断出WO3光降解MB的机理,当光照能量大于WO3的禁带宽度,电子会从价带激发到导带,在价带附近会产生空穴h+,电子捕获氧分子产生超氧自由基(·O2-),价带中的h+氧化水分子产生羟基自由基(·OH),·O2-、e-和·OH氧化吸附在WO3表面上的MB分子,最终大部分的MB分子被氧化,使得亚甲基蓝溶液脱色。
由上可知,生物遗态的WO3在降解亚甲基蓝溶液方面性能优良,且材料来源简单,充分利用稻壳自身结构,减少处理染料废水成本,具有潜在的开发应用前景。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种生物遗态的WO3光催化剂的制备方法,其特征在于,包括以下步骤:将稻壳浸渍到钨源溶液中,固液分离后对所得固体物料进行焙烧,得到生物遗态的WO3光催化剂。
2.根据权利要求1所述的制备方法,其特征在于,所述浸渍前,还包括对稻壳依次进行清洗、酸浸和氨水抽提。
3.根据权利要求2所述的制备方法,其特征在于,所述酸浸采用的酸液为盐酸,所述盐酸的质量浓度为5~7%;酸浸的时间为3~5h。
4.根据权利要求2所述的制备方法,其特征在于,进行氨水抽提时所用氨水的质量浓度为5~7%,抽提时间为3~4h。
5.根据权利要求1所述的制备方法,其特征在于,所述钨源溶液的钨源为钨酸钙或氯化钨;所述钨源溶液的溶剂为乙醇或甲醇;所述钨源溶液中钨源和溶剂的比例为(0.1~5)g:40mL。
6.根据权利要求5所述的制备方法,其特征在于,所述浸渍的时间为46~50h。
7.根据权利要求1所述的制备方法,其特征在于,所述焙烧的温度为540~550℃,保温时间为4~6h;所述焙烧的氛围为空气氛围。
8.根据权利要求7所述的制备方法,其特征在于,自室温升至所述焙烧的温度,升温速率为1.5~2℃/min。
9.权利要求1~8任一项所述制备方法制备得到的生物遗态的WO3光催化剂。
10.权利要求9所述生物遗态的WO3光催化剂在处理亚甲基蓝废水中的应用。
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CN114054008A (zh) * | 2021-10-29 | 2022-02-18 | 吉林建筑大学 | 一种光催化剂及其制备方法和应用 |
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