CN112441884B - 一种钽基半导体光催化甲醇偶联制乙二醇的方法 - Google Patents
一种钽基半导体光催化甲醇偶联制乙二醇的方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 144
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- 238000000034 method Methods 0.000 title claims abstract description 22
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- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 20
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims abstract description 5
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 23
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 11
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Abstract
一种钽基半导体光催化甲醇偶联制乙二醇的方法,涉及能源催化领域。将光催化剂分散到溶液中,除去反应体系中的氧气,然后进行光催化反应即可制得乙二醇;其中,所述溶液为甲醇或甲醇‑水体系,所述光催化剂为钽基半导体光催化剂及修饰的钽基半导体光催化剂中的至少一种。具有绿色、高效、反应条件温和等特点。
Description
技术领域
本发明涉及能源催化领域,尤其涉及一种钽基半导体光催化甲醇偶联制乙二醇的方法。
背景技术
乙二醇是一种重要的能源化工原料,广泛应用于生产聚酯纤维、涤纶纤维、吸湿剂、表面活性剂、化妆品等。近十年来,我国乙二醇进口需求量不断增加,且长期依赖于进口。2019年1-9月乙二醇累计进口742.15万吨,乙二醇的对外依赖度为度为59.64%。目前乙二醇的生产方法主要有石油路线和煤基路线。石油路线主要是指将石油裂解产生乙烯,乙烯氧化生成环氧乙烷,环氧乙烷跟水反应生成乙二醇。而煤基路线是指将煤转化成合成气,合成气羰基化转化成草酸酯,草酸酯加氢生成乙二醇。目前,这两种途径都是在高温、高压下进行,具有反应条件苛刻、工艺复杂、能耗高等缺点。
光催化技术是一种绿色、无污染、高效的高级氧化技术。因此,采用光催化技术将价格低廉、易得的甲醇选择性脱氢、偶联制备乙二醇是非常有意义的。Shozo anagida课题组(J.Chem.Soc.Chem.Commun.,1984,21-22)以ZnS为光催化剂,在紫外光照射下,将甲醇转化成乙二醇。但是,该反应存在反应活性低、选择性差等缺点。王野课题组(NatureCommun.,2018,9,1181;CN106831331A;Chem.Commun.,2020,56,1776)用MoS2/CdS、CoP/Zn2In2S5等光催化剂,在可见光照射下,可将甲醇选择性脱氢偶联制乙二醇。然而,硫化物光催化剂不稳定,易发生光腐蚀。因此,它的应用受到限制。
发明内容
本发明的目的在于解决现有技术中的上述问题,提供一种钽基半导体光催化甲醇偶联制乙二醇的方法,具有绿色、高效、乙二醇选择性高等优点。
为达到上述目的,本发明采用如下技术方案:
一种钽基半导体光催化甲醇偶联制乙二醇的方法,将光催化剂分散到溶液中,除去反应体系中的氧气,然后进行光催化反应即可制得乙二醇;其中,所述溶液为甲醇或甲醇-水体系,所述光催化剂为钽基半导体光催化剂及修饰的钽基半导体光催化剂中的至少一种。
所述钽基半导体光催化剂选自Ta2O5、TaON、Ta3N5、LiTaO3、NaTaO3、KTaO3、Rb4Ta6O17、MgTa2O6、CaTa2O6、SrTa2O6、BaTa2O6、K3Ta3Si2O13、HNdTa2O7、InTaO4、Sn2Ta2O7中的至少一种。
所述修饰的钽基半导体光催化剂的修饰方法包括金属离子掺杂、非金属掺杂、负载金属、负载金属氧化物、负载金属硫化物。
所述金属离子掺杂的量按质量百分比计为0.01%~20%;所述金属离子为La、Zr、Bi、Cu、Ir、Ca、Rb、Pr、Sm、Ce、Nd中的至少一种。
所述非金属掺杂的量按质量百分比计为0.01%~20%;所述非金属为C、N、O、S、F中的至少一种。
所述负载金属的量按质量百分比计为0.01%~20%;所述金属为Pt、Rh、Ni、Co、Ir、Pd、Au、Ag、Cu中的至少一种。
所述负载金属氧化物的量按质量百分比计为0.01%~10%,所述金属氧化物为NiO、Cu2O、MnO2、Fe2O3、V2O5、CeO2、TiO2、MoO3、WO3中的至少一种。
所述负载金属硫化物的量按质量百分比计为0.01%~10%;所述金属硫化物为MoS2、In2S3、CdS、CuS、NiS、FeS、PdS、PtS、WS2中的至少一种。
所述除去反应体系中的氧气是指超声脱气、真空排气、通入氮气,以保持惰性气氛;所述甲醇-水体系中,甲醇的体积分数可大于10%;光催化反应中所使用光源为氙灯、LED灯、汞灯、卤钨灯、太阳光中的一种。
所述催化剂的形貌为纳米颗粒、纳米方块、纳米球、纳米线、纳米棒、纳米花、纳米片中的至少一种。
所述钽基半导体光催化剂可通过高温固相反应法、熔盐法、水热法、溶胶-凝胶法制备。
相对于现有技术,本发明技术方案取得的有益效果是:
本发明以钽基半导体为光催化剂,在光照射下,反应一段时间,可以将甲醇转化为乙二醇,反应在氮气气氛下进行,具有绿色、环保、高效、反应条件温和等特点。相比较于CdS、P25,本发明采用的钽基半导体催化剂具有更高的活性以及更高的选择性。钽基半导体光催化剂稳定性较好,能够选择性活化甲醇的碳氢键,对甲醇和反应中间体的吸附较弱,有利于中间体的脱附偶联生成乙二醇,钽基半导体是一种非常有潜力的甲醇光催化偶联制乙二醇的光催化剂。
附图说明
图1为Ta2O5的扫描电镜图。
图2为N-Ta2O5的扫描电镜图。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白,以下结合附图和实施例,对本发明做进一步详细说明。
实施例1
称取一定量的Ta2O5置于瓷舟中,然后将瓷舟转移至管式炉中,以5℃/min升温至850℃,通入不同比例(0,5%,10%,67%,100%)的NH3,保持6h,得到不同氮含量的Ta2O5,分别标记为Ta2O5、N-Ta2O5-5%、N-Ta2O5-10%、N-Ta2O5-67%、N-Ta2O5-100%。如图1所示,为Ta2O5的扫描电镜图。
对上述催化剂分别进行催化性能测试:
称取10mg上述制备的催化剂加入至反应管中,加入4.5mL甲醇和0.5mL水,超声分散均匀,抽气,通入氮气。开启氙灯,进行光催化反应12h。反应冷却后,用液相色谱对产物进行分析。液相分析结果表明Ta2O5、N-Ta2O5-5%、N-Ta2O5-10%、N-Ta2O5-67%、N-Ta2O5-100%光催化甲醇偶联生成乙二醇的生成速率分别为0.46mmol g-1h-1、2.0mmol g-1h-1、4.0mmolg-1h-1、1.1mmol g-1h-1、0.2mmol g-1h-1;相应的选择性分别为71%、62%、71%、54%、76%。相比较P25(对比例1)、CdS(对比例2),上述催化剂具有更好的光催化甲醇偶联制乙二醇的活性。
实施例2
称取一定量的Ta2O5置于瓷舟中,然后将瓷舟转移至管式炉中,以5℃/min升温至850℃,通入10%的NH3,保持6h,得到氮掺杂的Ta2O5,记为N-Ta2O5。如图2所示,为N-Ta2O5的扫描电镜图。
对上述催化剂进行催化性能测试:
称取10mg上述催化剂加入至反应管中,加入4.5mL甲醇和0.5mL水,超声分散均匀,抽气,通入氮气。开启氙灯,进行光催化反应60h。反应冷却后,用液相色谱对产物进行分析。液相分析结果表明乙二醇的生成速率3.95mmol g-1h-1,乙二醇的选择性为70%。相较对比例3中的CdS催化剂,N-Ta2O5催化剂具有更好的催化活性和稳定性。
实施例3
将Ta2O5分别与碳酸盐(Li2CO3、Na2CO3、K2CO3)以1:1.05的摩尔比进行混合,再将混合物与等质量的NaCl/KCl的混合物(NaCl:KCl的质量比为0.45:0.55)进行混合。将上述混合物转移至瓷舟内,将瓷舟放置于管式炉中,以2℃/min升温至750℃,保持3h。待冷却后,用超纯水洗去表面未反应的离子,80℃烘干,即可得到LiTaO3、NaTaO3、KTaO3。
对上述催化剂分别进行催化性能测试:
称取10mg上述催化剂加入至反应管中,加入4.5mL甲醇和0.5mL水。超声分散均匀,抽气,通入氮气。开启氙灯,进行光催化反应。反应结束后,用滤膜进行过滤,用液相色谱进行产物分析。液相分析结果表明LiTaO3、NaTaO3、KTaO3光催化甲醇偶联生成乙二醇的生成速率分别为0.14mmol g-1h-1、0.21mmol g-1h-1、0.05mmol g-1h-1;相应的选择性分别为71%、17%、3%。
实施例4
将0.5g Ta2O5和3.0mL HF加入至20mL反应釜内,升温至140℃,以完全溶解Ta2O5。待冷却至室温,将20mL NH3·H2O逐滴加入上述溶液,产生白色的沉淀。将上述白色沉淀离心,洗涤,60℃烘干,得到Ta2O5·nH2O。将0.01g Ta2O5·nH2O和0.4g NaOH分散于14mL不同比例(乙二醇:水的比例分别为0:14、3:11、5:9)的乙二醇水溶液。将上述前驱体转移至反应釜,200℃反应12h,待冷却至室温,离心,用去离子水合乙醇洗涤三次,烘干,得到立方块、八面体以及纳米球状的NaTaO3,分别标记为NaTaO3-EG-0、NaTaO3-EG-3、NaTaO3-EG-5。
对上述催化剂分别进行催化性能测试:
将制备得到的不同形貌的NaTaO3分别加入至反应管内,加入4.5mL甲醇和0.5mL水,超声分散均匀,抽气,通入氮气。开启汞灯,进行光催化反应。反应12h后,待冷却至室温后,用液相色谱对产物进行分析。液相分析结果表明NaTaO3-EG-0、NaTaO3-EG-3、NaTaO3-EG-5光催化甲醇偶联制乙二醇的生成速率为0.19mmol g-1h-1、0.15mmol g-1h-1、0.26mmol g-1h-1,乙二醇的选择性分别为17%、6%、7%。
实施例5
将0.6g NaOH和0.442g Ta2O5分散于20mL超纯水,搅拌1h,转移至高压反应釜,140℃反应12h。反应完后,离心,用超纯水洗涤至中性,烘干,得到NaTaO3。进一步通过光沉积的方法负载Pt助催化剂,得Pt/NaTaO3催化剂。
对上述催化剂进行催化性能测试:
称取10mg催化剂加入至反应管中,加入4.5mL甲醇和0.5mL水,超声分散均匀,抽气,通入氮气。开启汞灯,光催化反应12h。待反应液冷却后,用滤膜过滤,用液相色谱对产物进行分析。分析结果表明Pt/NaTaO3光催化甲醇偶联制乙二醇的生成速率为1.2mmol g-1h-1,乙二醇的选择性为35%,甲醇氧化的其他产物主要为甲醛。
实施例6
将0.6g NaOH和0.442g Ta2O5分散于20mL超纯水,搅拌1h,转移至高压反应釜,140℃反应12h。反应完后,离心,用超纯水洗涤至中性,烘干,得到NaTaO3。称取0.1g NaTaO3置于瓷舟中,放入管式炉中,通入10%的NH3,以5℃/min升温至750℃,保持2h,待冷却至室温,取出,得到N-NaTaO3。进一步在N-NaTaO3上负载MoO3,制得MoO3/N-NaTaO3催化剂。
对上述催化剂进行催化性能测试:
称取10mg MoO3/N-NaTaO3,加入至反应管中,加入4.5mL甲醇和0.5mL水,超声分散均匀,抽气,通入氮气。开启氙灯,进行光催化反应。反应12h后,待反应液冷却至室温,用滤膜过滤,用液相色谱对产物进行分析。液相分析结果表明MoO3/N-NaTaO3光催化甲醇偶联制乙二醇的生成速率为0.68mmol g-1h-1,乙二醇的选择性为62%。
实施例7
将0.6g NaOH和0.442g Ta2O5分散于20mL超纯水,搅拌1h,转移至高压反应釜,140℃反应12h。反应完后,离心,用超纯水洗涤至中性,烘干,得到NaTaO3。称取0.05g NaTaO3加入至反应管中,加入4.5mL甲醇和0.4mL水以及100μL 5mg/L的氯化镍溶液,超声分散均匀,抽气,通入氮气,开启氙灯,进行光沉积。反应30min后,离心,洗涤,冷冻干燥,得到Ni/NaTaO3。
对上述催化剂进行催化性能测试:
称取10mg Ni/NaTaO3于反应管中,加入4.5mL甲醇和0.5mL水,超声分散均匀,抽气,通入氮气。开启氙灯,进行光催化反应。反应12h后,待反应液冷却至室温,用滤膜过滤,用液相色谱对产物进行分析。液相分析结果表明乙二醇的生成速率为,选择性为0.65mmolg-1h-1,乙二醇的选择性为70%。
实施例8
将Ta2O5和Na2CO3以摩尔比为1:1.05进行混合,再分别加入摩尔百分比1%(以Ta2O5为标准)的La2O3、SrCO3进行混合,研磨30分钟,将研磨后的粉末催化剂转移至刚玉瓷舟,再将其置于马弗炉中,以5℃/min升温至900℃,保持1h,再以5℃/min升温至1150℃,保持10h。待降至室温,取出催化剂,用超纯水将催化剂表面残留的离子清洗掉,80℃烘干,分别得到La-NaTaO3和Sr-NaTaO3。然后通过实施例1的方法对催化剂进行掺氮,得N-La-NaTaO3和N-Sr-NaTaO3催化剂。
对上述催化剂分别进行催化性能测试:
称取10mg上述催化剂置于反应管中,移取4.5mL甲醇和0.5mL水。超声分散,抽气、通入氮气。开启氙灯,反应12h。反应后,用滤膜过滤,进行液相色谱。液相结果表明N-La-NaTaO3和N-Sr-NaTaO3光催化甲醇偶联生成乙二醇的生成速率分别为1.7mmol g-1h-1、2.1mmol g-1h-1,选择性分别为74%、77%。
对比例1
称取一定量的P25放置于坩埚中,将坩埚转移至马弗炉中,以5℃/min升温至450℃,保持2h。冷却至室温后,取10mg P25置于反应管中,移取4.5mL甲醇和0.5mL水。超声分散,抽气、通入氮气。开启氙灯,反应12h。反应后,用滤膜过滤,进行液相色谱。液相结果表明乙二醇的生成速率为0,选择性为0,甲醇氧化的主要产物为甲醛。
对比例2
将4.62g CdCl2·2H2O和4.62g CH4NH2S溶于60mL乙二胺,将此溶液转移至高压反应釜,160℃反应24h。离心,洗涤,干燥,得到CdS。称取10mg CdS置于反应管中,移取4.5mL甲醇和0.5mL水。超声分散,抽气、通入氮气。开启氙灯,反应12h。反应后,用滤膜过滤,进行液相色谱。液相结果表明CdS光催化甲醇偶联生成乙二醇的生成速率为0.46mmol g-1h-1,选择性为71%。
对比例3
将4.62g CdCl2·2H2O和4.62g CH4NH2S溶于60mL乙二胺,将此溶液转移至高压反应釜,160℃反应24h。离心,洗涤,干燥,得到CdS。称取10mg CdS置于反应管中,移取4.5mL甲醇和0.5mL水。超声分散,抽气、通入氮气。开启氙灯,反应60h。反应后,用滤膜过滤,进行液相色谱。液相结果表明CdS光催化甲醇偶联生成乙二醇的生成速率为0.38mmol g-1h-1,选择性为68%。
本发明以钽基半导体为光催化剂,在光照射下,反应一段时间,可以将甲醇转化为乙二醇,反应在氮气气氛下进行,具有绿色、环保、高效、反应条件温和等特点。相比较于CdS、P25,本发明采用的钽基半导体催化剂具有更高的活性以及更高的选择性。钽基半导体光催化剂稳定性较好,能够选择性活化甲醇的碳氢键,对甲醇和反应中间体的吸附较弱,有利于中间体的脱附偶联生成乙二醇,钽基半导体是一种非常有潜力的甲醇光催化偶联制乙二醇的光催化剂。
Claims (4)
1.一种钽基半导体光催化甲醇偶联制乙二醇的方法,其特征在于:将光催化剂分散到溶液中,除去反应体系中的氧气,然后进行光催化反应即可制得乙二醇;其中,所述溶液为甲醇或甲醇-水体系,所述光催化剂为Ta2O5、氮掺杂的Ta2O5、氮掺杂的La-NaTaO3和氮掺杂的Sr-NaTaO3中的至少一种。
2.如权利要求1所述的一种钽基半导体光催化甲醇偶联制乙二醇的方法,其特征在于:所述氮掺杂的量按质量百分比计为0.01%~20%。
3.如权利要求1所述的一种钽基半导体光催化甲醇偶联制乙二醇的方法,其特征在于:所述除去反应体系中的氧气是指依次经过超声脱气、真空排气、通入氮气,以保持惰性气氛;所述甲醇-水体系中,甲醇的体积分数大于10%;光催化反应中所使用光源为氙灯、LED灯、汞灯、卤钨灯、太阳光中的一种。
4.如权利要求1所述的一种钽基半导体光催化甲醇偶联制乙二醇的方法,其特征在于:所述催化剂的形貌为纳米颗粒、纳米方块、纳米球、纳米线、纳米棒、纳米花、纳米片中的至少一种。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103864576A (zh) * | 2014-03-28 | 2014-06-18 | 厦门大学 | 一种光催化甲醛转化制备乙二醇的方法 |
CN106831331A (zh) * | 2016-12-29 | 2017-06-13 | 厦门大学 | 一种光催化转化甲醇制备乙二醇的方法 |
CN106984353A (zh) * | 2017-03-22 | 2017-07-28 | 浙江理工大学 | 一种掺杂半导体光催化剂的方法 |
CN107739302A (zh) * | 2017-11-07 | 2018-02-27 | 中国科学院山西煤炭化学研究所 | 一种光催化甲醇转化合成甲缩醛和乙二醇的方法 |
CN107827709A (zh) * | 2017-11-07 | 2018-03-23 | 中国科学院山西煤炭化学研究所 | 一种光催化乙醇转化合成巴豆醇的方法 |
CN108503509A (zh) * | 2018-03-23 | 2018-09-07 | 上海大学 | 一种光催化甲醛和甲醇偶联制备乙二醇的方法 |
CN110746271A (zh) * | 2019-09-23 | 2020-02-04 | 厦门大学 | 一种光催化甲醇脱氢偶联制备乙二醇的方法 |
-
2020
- 2020-11-30 CN CN202011374705.1A patent/CN112441884B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103864576A (zh) * | 2014-03-28 | 2014-06-18 | 厦门大学 | 一种光催化甲醛转化制备乙二醇的方法 |
CN106831331A (zh) * | 2016-12-29 | 2017-06-13 | 厦门大学 | 一种光催化转化甲醇制备乙二醇的方法 |
CN106984353A (zh) * | 2017-03-22 | 2017-07-28 | 浙江理工大学 | 一种掺杂半导体光催化剂的方法 |
CN107739302A (zh) * | 2017-11-07 | 2018-02-27 | 中国科学院山西煤炭化学研究所 | 一种光催化甲醇转化合成甲缩醛和乙二醇的方法 |
CN107827709A (zh) * | 2017-11-07 | 2018-03-23 | 中国科学院山西煤炭化学研究所 | 一种光催化乙醇转化合成巴豆醇的方法 |
CN108503509A (zh) * | 2018-03-23 | 2018-09-07 | 上海大学 | 一种光催化甲醛和甲醇偶联制备乙二醇的方法 |
CN110746271A (zh) * | 2019-09-23 | 2020-02-04 | 厦门大学 | 一种光催化甲醇脱氢偶联制备乙二醇的方法 |
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