CN107335438A - CuOx‑NiO共修饰TiO2光催化高效还原脱氯材料的制备方法 - Google Patents
CuOx‑NiO共修饰TiO2光催化高效还原脱氯材料的制备方法 Download PDFInfo
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Abstract
本发明涉及材料制备领域,旨在提供一种CuOx‑NiO共修饰TiO2光催化高效还原脱氯材料的制备方法。是以钛酸四丁酯为TiO2前驱体,利用HF的蚀刻性能,采用水热法制备纳米片状TiO2晶体。再以浸渍法在催化剂表面负载NiO;利用TiO2的光还原能力,加入含Cu2+盐溶液,在光下还原二价铜并负载于TiO2表面,之后通过煅烧的方法,增强催化剂表面Cu的活性,最终合成具有协同效应的双金属氧化物共修饰纳米片状TiO2催化剂。本发明合成了双金属氧化物共负载纳米片状TiO2催化剂,其片状结构提高了催化剂比表面积,光催化反应位点增多,同时利用双金属氧化物与催化剂三者协同相互作用,实现光生电子的高效利用,克服了块状TiO2催化剂效率低的问题,光催化脱氯效率大大提高。
Description
技术领域
本发明涉及一种CuOx-NiO共修饰的TiO2光催化还原高效电子转移材料的制备方法,用于脱除水中含氯有机物,属于材料制备及环境技术领域。
背景技术
近年来,随着有机化工、氯制品化工的不断发展,大量含氯有机副产物如三氯乙烯、2,4-二氯苯酚等被排放到大气中。绝大部分含氯有机物难以生物降解、在环境中稳定存在,并且会从大气进入土壤、水环境中,特别是导致对地下水源的污染,具有致癌、致畸效应,对人体危害极大。
目前,水中含氯有机物处理方法主要有以下几种。
物理吸附。活性炭吸附和曝气吹脱是除去水中含氯有机物的重要物理方法。前者利用活性炭较大的比表面积吸附水中含氯有机物,从而实现污染物去除。后者通过向水中曝气使含氯有机物由液相扩散到气相中。两种方法均可实现水中含氯有机物的有效去除,但仅仅将含氯有机物转移至固相、气相中,无法将其分解为无害物质,会造成严重二次污染。
生物分解。生物法是利用微生物生长代谢过程中产生的生物酶分解水中含氯有机物。生物法脱氯技术具有处理效率高、费用低以及降解彻底的优点。但自然界相对应微生物种类较少,微生物培育周期长,工艺条件难以控制并且占地面积较大。
化学降解。零价铁还原降解水中含氯有机物是一种重要的化学处理手段。由于普通零价铁粉还原活性不高,研究者通过制备纳米级铁粉并在表面负载金属提高其还原活性。如发明专利CN103086494A利用贵金属Pd和EDTA的良好给电子特性,通过合成钯/铁颗粒并加入EDTA溶液在厌氧环境下实现水中含氯有机物的快速去除。专利CN101298049A公布了一种钯/泡沫金属催化剂的制备方法,结合泡沫金属的多孔结构与Pd贵金属的强还原性,有效去除水中氯酚等氯代芳烃。然而,零价金属还原过程中会引起pH上升,生成氢氧化物沉淀,进而覆盖催化剂表面降低反应活性同时提高溶液色度。此外,为提高还原性能使用的贵金属电子供体,成本较高,存在二次污染风险。
近年来,光催化脱氯作为一种新兴技术受到广泛关注。光催化技术利用半导体内部产生的具有强氧化还原能力的电子-空穴对,通过对污染物的氧化或还原,实现温和条件下污染物的高效去除。TiO2因其化学稳定性强、无生物毒性以及成本低廉的特点得到广泛研究。Liu等(Chemical Engineering Journal,2012,181-182,189-195)利用化学法合成了Fe负载TiO2催化剂,利用催化剂光激发下产生的空穴以及活性自由基高效去除水中2,4-二氯苯酚,反应3h后,污染物降解率达到100%,且总有机碳降低到20%。光催化氧化过程产生的活性自由基对污染物的去除效果明显,但无法实现污染物的完全矿化,甚至生成毒性更强的中间产物,因此通过光催化还原技术,利用还原性强的电子脱除氯元素为无机氯,并回收相应烃类产物,避免中间产物的生产,极大减小了环境风险,具有更大的应用价值。通过对催化剂修饰改性提高光生电子的有效利用是光催化还原技术的研究重点。目前尚未查到直接应用于还原脱氯的光催化剂相关专利。在光催化还原脱氯研究中,贵金属因其具有等离子体共振效应,可以高效转移电子,研究较多。Tanaka等(The Journal of PhysicalChemical C,2013,117(33),16983-16989)通过两步光还原沉积法在TiO2表面负载Au/Pd核壳结构,利用Au/Pd结构快速的界面电子转移效应,在高效去除溶液中氯苯同时,实现苯的回收利用。然而贵金属成本高,对环境存在潜在的污染。
在研究中发现,在催化剂表面负载二元非贵金属,如过渡金属铜、镍等,可产生协同效应,实现电子高效利用,显著提升催化剂光还原能力,有望取代光催化还原脱氯领域贵金属的地位。
发明内容
本发明要解决的技术问题是,克服现有技术中的不足,提供一种CuOx-NiO共修饰TiO2光催化高效还原脱氯材料的制备方法。
为解决技术问题,本发明的解决方案是:
提供一种CuO-NiO共修饰的TiO2光催化还原高效电子转移材料的制备方法,包括以下步骤:
(1)水热法制备纳米片状TiO2
取40wt%的HF溶液1~5mL,逐滴加入到25mL钛酸四丁酯中;搅拌2h后移至水热釜中,置于烘箱中并升温至180℃保持24h;所得白色固体先用去离子水清洗三次,再用无水乙醇清洗三次后,放入烘箱中烘干;固体粉末经研磨后,放入马弗炉中350℃煅烧2h,冷却后得到纳米片状TiO2催化剂;
(2)浸渍法制备NiO负载纳米片状TiO2
取0.05mol/L的NaOH溶液50mL,将步骤(1)得到的纳米片状TiO2催化剂加至其中,搅拌下滴加含镍化合物溶液,继续搅拌6h;弃上清液,取沉淀物加入去离子水,超声分散后离心;重复该操作直至上清液pH=7;滤饼烘干后研磨,再置于马弗炉中升温至450℃煅烧2h,冷却后得到NiO负载纳米片状TiO2催化剂;
控制含镍化合物溶液的用量,使NiO负载纳米片状TiO2催化剂中,TiO2∶Ni的质量比为100∶(0.05~2);
(3)光还原法制备CuO-NiO双金属氧化物修饰纳米片状TiO2
取步骤(2)中得到的NiO负载纳米片状TiO2催化剂,加至含铜化合物溶液中,超声混合10min;继续加入5mL丙三醇,并加入去离子水使混合溶液的总体积为100mL;通入氩气0.5h后,氙灯光照2h,全程保持搅拌;光照结束后离心处理,弃上清液,沉淀物烘干后研磨,再置于马弗炉中升温至350℃煅烧2h;冷却后得到CuOx-NiO双金属氧化物共修饰纳米片状TiO2催化剂;
控制含铜化合物溶液的用量,使CuOx-NiO共修饰的TiO2光催化还原高效电子转移材料中,TiO2∶Ni∶Cu的质量比为100∶(0.05~2)∶(0.4~1.5)。
本发明步骤(1)中的升温速率为2~5℃/min。
本发明步骤(2)中,所述含镍化合物溶液是Ni(NO3)2·6H2O、NiCl2·6H2O或NiSO4·6H2O的水溶液中的一种或多种。
本发明步骤(3)中,所述含铜化合物溶液是Cu(NO3)2·3H2O、CuCl2·2H2O或CuSO4·5H2O的水溶液中的一种或多种。
本发明步骤(3)中,制备得到的CuOx-NiO共修饰的TiO2光催化还原高效电子转移材料中,Ni和Cu的负载量之和与TiO2的质量的比例为(0.45~3):100。
本发明步骤(3)中的氙灯功率为300W,发射的紫外-可见光波长范围为350-780nm。
本发明的实现原理:
本发明采用水热法,以钛酸四丁酯为TiO2前驱体,通过控制反应温度与时间,利用HF的蚀刻性能,制备出了纳米片状TiO2晶体。在此基础上,采用浸渍法在催化剂表面负载NiO;利用TiO2的光还原能力,加入含Cu2+盐溶液,在光下还原二价铜并负载于TiO2表面,之后通过煅烧的方法,增强催化剂表面Cu的活性,最终合成具有协同效应的双金属氧化物共修饰纳米片状TiO2催化剂。
与现有技术相比,本发明的有益效果在于:
1、本发明利用水热法、浸渍法和光还原沉积法合成了双金属氧化物共负载纳米片状TiO2催化剂,其片状结构提高了催化剂比表面积,光催化反应位点增多,同时利用双金属氧化物与催化剂三者协同相互作用,实现光生电子的高效利用,克服了块状TiO2催化剂效率低的问题,相较于商业化催化剂P25,光催化脱氯效率大大提高。
2、本发明中采用过渡金属盐类前驱体制备了高效光催化剂,成本低廉,有助于推广使用。
附图说明
图1为不同催化剂的扫描电镜图;
图中,a为TiO2;b为CuOx-TiO2;c为NiO-TiO2;d为CuOx-NiO/TiO2。
图2为为不同催化剂的透射电镜图;
图中,a为NiO-TiO2的低倍透射电镜图、b为高倍透射电镜图;c为CuOx-NiO/TiO2的低倍透射电镜图、d为高倍透射电镜图。
图3为TiO2、CuOx-TiO2、NiO-TiO2和CuOx-NiO/TiO2吸附脱附曲线图;
图4为P25以及不同铜镍比CuOx-NiO/TiO2光催化脱氯效果图。
具体实施方式
下面结合实施例子来对本发明进一步详细说明,其中部分制备条件仅是作为典型情况的额说明,并非是对本发明的限定。
实施例1
(1)水热法制备纳米片状TiO2
将1mL HF(40wt%)的溶液逐滴滴加到装有25mL钛酸四丁酯的烧杯中,搅拌2h后,转移至水热釜中,放入烘箱,升温速率为2℃/min,升温至180℃保持24h。取出白色固体,先用去离子水清洗三次,再用无水乙醇清洗三次后,放入烘箱中烘干。得到的固体粉末经研磨后,放入马弗炉中350℃煅烧2h,冷却后得到纳米片状TiO2催化剂;
(2)浸渍法制备NiO负载纳米片状TiO2
取0.6g(1)中制备好的TiO2催化剂,加入50mL的NaOH溶液(质量浓度为0.05mol/L)中,保持磁力搅拌,滴加102μL 0.05mol/L的Ni(NO3)2溶液,磁力搅拌6h后,离心并倒掉上清液,取沉淀物加入去离子水,超声分散;继续离心直至上清液pH=7;滤饼放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中,450℃条件下煅烧2h,冷却后得到NiO负载纳米片状TiO2催化剂;
(3)光还原法制备CuOx-NiO双金属氧化物共修饰纳米片状TiO2
取0.6g(2)中制备好的催化剂与3777μL 0.01mol/L CuCl2溶液混合超声10min,加入5mL丙三醇和一定量的去离子水(保证溶液总体积为100mL),氙灯光照2h,全程保持磁力搅拌(氙灯光照的功率为300W,其出射光谱波长范围在350~780nm)。光照之前,通入高纯氩气(纯度大于99.999%)0.5h。光照结束后,通过离心处理后,倒掉上清液,放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中350℃煅烧2h。冷却后得到CuOx-NiO双金属氧化物共修饰纳米片状TiO2催化剂;
经测定,所制备的双金属氧化物共修饰TiO2催化剂中,Cu、Ni的负载量之和与TiO2质量比为0.45:100。其中,Ni与TiO2的质量比为0.05:100,Cu与TiO2的质量比为0.4:100。
实施例2
(1)水热法制备纳米片状TiO2
将2mL HF(40wt%)的溶液逐滴滴加到装有25mL钛酸四丁酯的烧杯中,搅拌2h后,转移至水热釜中,放入烘箱,升温速率为3℃/min,升温至180℃保持24h。取出白色固体先用去离子水清洗三次,再用无水乙醇清洗三次后,放入烘箱中烘干。得到的固体粉末经研磨后,放入马弗炉350℃煅烧2h,冷却后得到纳米片状TiO2催化剂;
(2)浸渍法制备NiO负载纳米片状TiO2
取0.6g(1)中制备好的TiO2催化剂加入50mL的NaOH溶液(质量浓度为0.05mol/L)中,保持磁力搅拌,滴加816μL 0.05mol/L NiCl2溶液,磁力搅拌6h后,离心至悬浮液pH=7,倒掉上清液,取沉淀物加入去离子水,超声分散;继续离心直至上清液pH=7;滤饼放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中,450℃条件下煅烧2h,冷却后得到NiO负载纳米片状TiO2催化剂;
(3)光还原法制备CuOx-NiO双金属氧化物共修饰纳米片状TiO2
取0.6g(2)中制备好的催化剂与7554μL 0.01mol/L CuCl2溶液混合超声10min,加入5mL丙三醇和一定量的去离子水(保证溶液总体积为100mL),氙灯光照2h,全程保持磁力搅拌(氙灯光照的功率为300W,其出射光谱波长范围在350~780nm)。光照之前,通入高纯氩气(纯度大于99.999%)0.5h。光照结束后,通过离心处理后,倒掉上清液,放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中350℃煅烧2h。冷却后得到CuOx-NiO双金属氧化物共修饰纳米片状TiO2催化剂;
经测定,所制备双金属氧化物修饰TiO2催化剂中,Cu、Ni的负载量之和为1.2%。其中,Ni与TiO2的质量比为0.4%,Cu与TiO2的质量比为0.8%。
实施例3
(1)水热法制备纳米片状TiO2
将3mL HF(40wt%)的溶液逐滴滴加到装有25mL钛酸四丁酯的烧杯中,搅拌2h后,转移至水热釜中,放入烘箱,升温速率为5℃/min,升温至180℃保持24h.取出白色固体先用去离子水清洗三次,再用无水乙醇清洗三次后,放入烘箱中烘干。得到的固体粉末经研磨后,放入马弗炉350℃煅烧2h,冷却后得到纳米片状TiO2催化剂;
(2)浸渍法制备NiO负载纳米片状TiO2
取0.6g(1)中制备好的TiO2催化剂加入50mL NaOH溶液(质量浓度为0.05mol/L)中,保持磁力搅拌,滴加1020μL 0.05mol/L NiSO4溶液,磁力搅拌6h后,倒掉上清液,倒掉上清液,取沉淀物加入去离子水,超声分散;继续离心直至上清液pH=7;滤饼放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中,450℃条件下煅烧2h,冷却后得到NiO负载纳米片状TiO2催化剂;
(3)光还原沉积法制备CuOx-NiO双金属氧化物共修饰纳米片状TiO2
取0.6g(2)制备好的催化剂与14.2mL 0.01mol/L CuCl2溶液混合超声10min,加入5mL丙三醇和一定量的去离子水(保证溶液总体积为100mL),氙灯光照2h,全程保持磁力搅拌(氙灯光照的功率为300W,其出射光谱波长范围在350~780nm)。光照之前,通入高纯氩气(纯度大于99.999%)0.5h。光照结束后,通过离心处理后,倒掉上清液,放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中350℃煅烧2h。冷却后得到CuOx-NiO双金属氧化物共修饰纳米片状TiO2催化剂;
经测定,所制备的纳米片状TiO2大小为50nm,厚度为7nm。所制备双金属氧化物共修饰TiO2催化剂中,Cu、Ni的负载量之和为2%。其中,Ni与TiO2的质量比为0.5%,Cu与TiO2的质量比为1.5%。
实施例4
(1)水热法制备纳米片状TiO2
将4mL HF(40wt%)的溶液逐滴滴加到装有25mL钛酸四丁酯的烧杯中,搅拌2h后,转移至水热釜中,放入烘箱,升温速率为5℃/min,升温至180℃保持24h。取出白色固体先用去离子水清洗三次,再用无水乙醇清洗三次后,放入烘箱中烘干。得到的固体粉末经研磨后,放入马弗炉350℃煅烧2h,冷却后得到纳米片状TiO2催化剂;
(2)浸渍法制备NiO负载纳米片状TiO2
取0.6g(1)中制备好的TiO2催化剂加入50mL NaOH溶液(质量浓度为0.05mol/L)中,保持磁力搅拌,滴加3060μL 0.05mol/L Ni(NO3)2溶液,倒掉上清液,倒掉上清液,取沉淀物加入去离子水,超声分散;继续离心直至上清液pH=7;滤饼放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中,450℃条件下煅烧2h,冷却后得到NiO负载纳米片状TiO2催化剂;
(3)光还原沉积法制备CuOx-NiO双金属氧化物共修饰纳米片状TiO2
取0.6g(2)制备好的催化剂与9442μL 0.01mol/L CuSO4溶液混合超声10min,加入5mL丙三醇和一定量的去离子水(保证溶液总体积为100mL),氙灯光照2h,全程保持磁力搅拌(氙灯光照的功率为300W,其出射光谱波长范围在350~780nm)。光照之前,通入高纯氩气(纯度大于99.999%)0.5h。光照结束后,通过离心处理后,倒掉上清液,放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中350℃煅烧2h。冷却后得到CuOx-NiO双金属氧化物共修饰纳米片状TiO2催化剂;
经测定,所制备双金属氧化物共修饰TiO2催化剂中,Cu、Ni的负载量之和为2.5%。其中,Ni占TiO2的质量比为1.5%,Cu与TiO2的质量比为1.0%。
实施例5
(1)水热法制备纳米片状TiO2
将5mL HF(40wt%)的溶液逐滴滴加到装有25mL钛酸四丁酯的烧杯中,搅拌2h后,转移至水热釜中,放入烘箱,升温速率为5℃/min,升温至180℃保持24h。取出白色固体先用去离子水清洗三次,再用无水乙醇清洗三次后,放入烘箱中烘干。得到的固体粉末经研磨后,放入马弗炉350℃煅烧2h,冷却后得到纳米片状TiO2催化剂;
(2)浸渍法制备NiO负载纳米片状TiO2
取0.6g(1)中制备好的TiO2催化剂加入50mL NaOH溶液(质量浓度为0.05mol/L)中,保持磁力搅拌,滴加4080μL 0.05mol/L Ni(NO3)2溶液,磁力搅拌6h后,倒掉上清液,取沉淀物加入去离子水,超声分散;继续离心直至上清液pH=7;滤饼放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中,450℃条件下煅烧2h,冷却后得到NiO负载纳米片状TiO2催化剂;
(3)光还原沉积法制备CuOx-NiO双金属氧化物共修饰纳米片状TiO2
取0.6g(2)中制备好的催化剂与9442μL 0.01mol/L Cu(NO3)2溶液混合超声10min,加入5mL丙三醇和一定量的去离子水(保证溶液总体积为100mL),氙灯光照2h,全程保持磁力搅拌(氙灯光照的功率为300W,其出射光谱波长范围在350~780nm)。光照之前,通入高纯氩气(纯度大于99.999%)0.5h。光照结束后,通过离心处理后,倒掉上清液,放入烘箱中烘干。烘干的催化剂研磨后,置于马弗炉中350℃煅烧2h。冷却后得到CuOx-NiO双金属氧化物共修饰纳米片状TiO2催化剂;
经测定,所制备双金属氧化物负载TiO2催化剂中,Cu、Ni的负载量之和为3%。其中,Ni与TiO2的质量比为2.0%,Cu与TiO2的质量比为1.0%。
性能测试方法(脱氯效果实验)
由于光催化脱氯技术尚未进入工业化使用,此处采用已经商业化生产的P25型催化剂与本发明中制备的催化剂进行效果实验比较。
分别取商业化催化剂TiO2(P25)与实施例1-5制备的CuOx-NiO共修饰的TiO2光催化还原高效电子转移材料进行脱氯效果实验:
称取0.05g催化剂样品放入带循环夹套的自制光催化反应器中,放入磁力搅拌子,加入100mL 5v%丙三醇溶液,5g/L的2,4-二氯苯酚储备液400μL,使2,4-二氯苯酚的初始浓度为20mg/L。用硅胶垫垫于石英反应器盖和反应器中间,在连接处均匀涂抹真空硅脂,并在边缘缠绕密封胶带,使反应器密封。向反应器持续通高纯氩气(纯度大于99.999%)0.5h,排尽空气。之后迅速用密封垫及生料带密封取样口,并打开光源。实验所用光源为300W氙灯,出射光谱波长范围为350-780nm,光线从上到下照射。持续通入循环水,使反应体系的温度维持稳定。整个反应过程不断磁力搅拌,使样品一直处于悬浮状态。取样时间为0,10,20,30,40,50,60,70,80,90,100,110,120min。取得的样品用一次性微孔滤头(0.45μm聚醚砜膜)过滤。采用高效液相色谱(HPLC)分析2,4-二氯苯酚浓度。
测试结果说明
采用已商业化使用的P25催化剂作为对照,对实施例1-5所制备的高效电子转移CuOx-NiO/TiO2光催化材料按前述性能测试方法进行脱氯测试,其结果如图4所示。
从图中4可以看出,相较于商业化P25催化剂,本发明制备的双金属氧化物共修饰纳米片状TiO2表现出更好的光催化脱氯效果,表明光催化过程中光生电子的高效转移。当TiO2表面负载CuOx和NiO之后,脱氯效果显著增强。且当Ni占Ti的质量比为0.5%,Cu占TiO2的质量比为1.5%,脱氯效果最佳。
Claims (6)
1.一种CuO-NiO共修饰的TiO2光催化还原高效电子转移材料的制备方法,其特征在于,包括以下步骤:
(1)水热法制备纳米片状TiO2
取40wt%的HF溶液1~5mL,逐滴加入到25mL钛酸四丁酯中;搅拌2h后移至水热釜中,置于烘箱中并升温至180℃保持24h;所得白色固体先用去离子水清洗三次,再用无水乙醇清洗三次后,放入烘箱中烘干;固体粉末经研磨后,放入马弗炉中350℃煅烧2h,冷却后得到纳米片状TiO2催化剂;
(2)浸渍法制备NiO负载纳米片状TiO2
取0.05mol/L的NaOH溶液50mL,将步骤(1)得到的纳米片状TiO2催化剂加至其中,搅拌下滴加含镍化合物溶液,继续搅拌6h;弃上清液,取沉淀物加入去离子水,超声分散后离心;重复该操作直至上清液pH=7;滤饼烘干后研磨,再置于马弗炉中升温至450℃煅烧2h,冷却后得到NiO负载纳米片状TiO2催化剂;
控制含镍化合物溶液的用量,使NiO负载纳米片状TiO2催化剂中,TiO2∶Ni的质量比为100∶(0.05~2);
(3)光还原法制备CuO-NiO双金属氧化物修饰纳米片状TiO2
取步骤(2)中得到的NiO负载纳米片状TiO2催化剂,加至含铜化合物溶液中,超声混合10min;继续加入5mL丙三醇,并加入去离子水使混合溶液的总体积为100mL;通入氩气0.5h后,氙灯光照2h,全程保持搅拌;光照结束后离心处理,弃上清液,沉淀物烘干后研磨,再置于马弗炉中升温至350℃煅烧2h;冷却后得到CuOx-NiO双金属氧化物共修饰纳米片状TiO2催化剂;
控制含铜化合物溶液的用量,使CuOx-NiO共修饰的TiO2光催化还原高效电子转移材料中,TiO2∶Ni∶Cu的质量比为100∶(0.05~2)∶(0.4~1.5)。
2.根据权利要求1所述的方法,其特征在于,步骤(1)中的升温速率为2~5℃/min。
3.根据权利要求1所述的方法,其特征在于,步骤(2)中所述含镍化合物溶液是Ni(NO3)2·6H2O、NiCl2·6H2O或NiSO4·6H2O的水溶液中的一种或多种。
4.根据权利要求1所述的方法,其特征在于,步骤(3)中所述含铜化合物溶液是Cu(NO3)2·3H2O、CuCl2·2H2O或CuSO4·5H2O的水溶液中的一种或多种。
5.根据权利要求1所述的方法,其特征在于,步骤(3)中制备得到的CuOx-NiO共修饰的TiO2光催化还原高效电子转移材料中,Ni和Cu的负载量之和与TiO2的质量的比例为(0.45~3):100。
6.根据权利要求1所述的方法,其特征在于,步骤(3)中的氙灯功率为300W,发射的紫外-可见光波长范围为350-780nm。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110026249A (zh) * | 2019-04-17 | 2019-07-19 | 天津大学 | 一种用于常温降解VOCs的原子级“微纳催化胶囊” |
CN115845790A (zh) * | 2022-11-02 | 2023-03-28 | 江苏理工学院 | 一种氧化亚铜/氧化氮化碳复合材料及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104888770A (zh) * | 2015-04-30 | 2015-09-09 | 华中农业大学 | 一种负载金属Ag的C掺杂TiO2纳米颗粒可见光催化剂及其应用 |
CN105642331A (zh) * | 2016-02-25 | 2016-06-08 | 济南大学 | 一种二维纳米片状光催化剂的制备方法 |
-
2017
- 2017-06-27 CN CN201710503408.4A patent/CN107335438A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104888770A (zh) * | 2015-04-30 | 2015-09-09 | 华中农业大学 | 一种负载金属Ag的C掺杂TiO2纳米颗粒可见光催化剂及其应用 |
CN105642331A (zh) * | 2016-02-25 | 2016-06-08 | 济南大学 | 一种二维纳米片状光催化剂的制备方法 |
Non-Patent Citations (2)
Title |
---|
张旺喜 等: "AgBr/TiO2(001)纳米片可见光光催化剂的制备", 《湖北工业大学学报》 * |
路彦景 等: "CuO-NiO助催化剂对TiO2(P25)光催化活性的影响", 《无机化学学报》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110026249A (zh) * | 2019-04-17 | 2019-07-19 | 天津大学 | 一种用于常温降解VOCs的原子级“微纳催化胶囊” |
CN110026249B (zh) * | 2019-04-17 | 2021-05-25 | 天津大学 | 一种用于常温降解VOCs的原子级“微纳催化胶囊” |
CN115845790A (zh) * | 2022-11-02 | 2023-03-28 | 江苏理工学院 | 一种氧化亚铜/氧化氮化碳复合材料及其制备方法和应用 |
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