化工学报 ›› 2020, Vol. 71 ›› Issue (8): 3556-3564.DOI: 10.11949/0438-1157.20200172
李倩倩1(),唐思扬1(),岳海荣1,2,刘长军1,马奎1,钟山1,梁斌1,2
收稿日期:
2020-02-24
修回日期:
2020-05-22
出版日期:
2020-08-05
发布日期:
2020-08-05
通讯作者:
唐思扬
作者简介:
李倩倩(1994—),女,硕士研究生,基金资助:
Qianqian LI1(),Siyang TANG1(),Hairong YUE1,2,Changjun LIU1,Kui MA1,Shan ZHONG1,Bin LIANG1,2
Received:
2020-02-24
Revised:
2020-05-22
Online:
2020-08-05
Published:
2020-08-05
Contact:
Siyang TANG
摘要:
采用浸渍还原方法制备Pd-Rh/TiO2催化剂用于常温光催化CO2氧化乙烷脱氢制C2H4。研究不同Pd/Rh比催化剂的光反应性能,利用XRD、EDX-mapping、TEM、HRTEM、XPS技术表征催化剂表面和电子特性,通过UV-Vis、PL技术考察催化剂光响应性能,采用原位红外光谱技术分析Pd-Rh/TiO2光催化CO2氧化乙烷脱氢反应机理。研究表明,Pd-Rh双金属体系可有效提高光反应活性,光照下Pd和Rh金属之间存在内部电子转移的作用,降低了Pd表面的电子云密度,促进光生电子和空穴的分离,同时促进了C2H6和CO2在材料表面的吸附。Ar替换CO2的对比实验证明,反应中的CO2消耗H2,可消除催化剂表面积碳,促进C2H4生成。
中图分类号:
李倩倩, 唐思扬, 岳海荣, 刘长军, 马奎, 钟山, 梁斌. Pd-Rh/TiO2光催化CO2氧化乙烷脱氢研究[J]. 化工学报, 2020, 71(8): 3556-3564.
Qianqian LI, Siyang TANG, Hairong YUE, Changjun LIU, Kui MA, Shan ZHONG, Bin LIANG. Study on the photocatalytic oxidative dehydrogenation of ethane with CO2 over Pd-Rh /TiO2 catalyst[J]. CIESC Journal, 2020, 71(8): 3556-3564.
催化剂 | 活性/(μmol·(g cat)-1·h-1) | |||
---|---|---|---|---|
H2 | CH4 | C2H4 | CO | |
Pd | 122.2 | 126.1 | 226.0 | 74.8 |
1Pd-1Pt | 461.2 | 214.9 | 222.9 | trace |
1Pd-1Ni | 150.2 | 179.6 | 134.3 | trace |
1Pd-1Fe | 56.1 | 130.9 | 91.4 | 18.3 |
1Pd-1Cu | 417.1 | 149.9 | 294.2 | 25.2 |
1Pd-1Ru | 88.7 | 134.2 | 273.9 | 96.3 |
1Pd-1Ag | 798.3 | 134.2 | 510.7 | 23.8 |
1Pd-1Rh | 467.6 | 200.3 | 428.8 | 190.2 |
表1 Pd-M/TiO2双金属催化剂在CO2存在条件下的氧化乙烷脱氢性能评价
Table 1 Performance of oxidative dehydrogenation of ethane in the presence of CO2 over Pd-M /TiO2 catalysts
催化剂 | 活性/(μmol·(g cat)-1·h-1) | |||
---|---|---|---|---|
H2 | CH4 | C2H4 | CO | |
Pd | 122.2 | 126.1 | 226.0 | 74.8 |
1Pd-1Pt | 461.2 | 214.9 | 222.9 | trace |
1Pd-1Ni | 150.2 | 179.6 | 134.3 | trace |
1Pd-1Fe | 56.1 | 130.9 | 91.4 | 18.3 |
1Pd-1Cu | 417.1 | 149.9 | 294.2 | 25.2 |
1Pd-1Ru | 88.7 | 134.2 | 273.9 | 96.3 |
1Pd-1Ag | 798.3 | 134.2 | 510.7 | 23.8 |
1Pd-1Rh | 467.6 | 200.3 | 428.8 | 190.2 |
催化剂① | Pd负载量②/ %(质量) | Rh负载量②/ %(质量) | 活性(CO2下)/(μmol·(g cat)-1·h-1)③ | 活性(Ar下)/(μmol·(g cat) -1·h-1)④ | |||||
---|---|---|---|---|---|---|---|---|---|
H2 | CH4 | C2H4 | CO | H2 | CH4 | C2H4 | |||
Pd | 0.44 | 0 | 122.2 | 126.1 | 226.0 | 74.8 | 760.7 | 155.6 | 49.8 |
3Pd-1Rh | 0.25 | 0.16 | 284.9 | 57.9 | 284.6 | 134.1 | 947.0 | 144.7 | 68.1 |
1Pd-1Rh | 0.21 | 0.39 | 467.6 | 200.3 | 428.8 | 190.2 | 1102.9 | 134.8 | 72.6 |
1Pd-3Rh | 0.07 | 0.34 | 427.4 | 47.4 | 336.4 | 155.5 | 1533.8 | 136.8 | 161.6 |
Rh | 0.70 | 0 | 190.9 | 48.6 | 170.1 | 269.7 | 1908.9 | 147.8 | 43.9 |
P25 | —⑤ | — | 0.3 | 16.7 | 10.1 | trace | — | — | — |
表2 不同金属比例Pd-Rh/TiO2分别在CO2与Ar条件下的乙烷脱氢性能评价
Table 2 Ethane dehydrogenation performance under CO2 and Ar conditions with different metal ratios of Pd-Rh/TiO2
催化剂① | Pd负载量②/ %(质量) | Rh负载量②/ %(质量) | 活性(CO2下)/(μmol·(g cat)-1·h-1)③ | 活性(Ar下)/(μmol·(g cat) -1·h-1)④ | |||||
---|---|---|---|---|---|---|---|---|---|
H2 | CH4 | C2H4 | CO | H2 | CH4 | C2H4 | |||
Pd | 0.44 | 0 | 122.2 | 126.1 | 226.0 | 74.8 | 760.7 | 155.6 | 49.8 |
3Pd-1Rh | 0.25 | 0.16 | 284.9 | 57.9 | 284.6 | 134.1 | 947.0 | 144.7 | 68.1 |
1Pd-1Rh | 0.21 | 0.39 | 467.6 | 200.3 | 428.8 | 190.2 | 1102.9 | 134.8 | 72.6 |
1Pd-3Rh | 0.07 | 0.34 | 427.4 | 47.4 | 336.4 | 155.5 | 1533.8 | 136.8 | 161.6 |
Rh | 0.70 | 0 | 190.9 | 48.6 | 170.1 | 269.7 | 1908.9 | 147.8 | 43.9 |
P25 | —⑤ | — | 0.3 | 16.7 | 10.1 | trace | — | — | — |
图1 催化剂稳定性测试和积碳检测(稳定性测试条件:温度 298 K;压力0.2 MPa;反应气C2H6∶CO2=1∶1;1Pd-1Rh催化剂用量25 mg循环利用)
Fig.1 Stability test and carbon deposition test(stability test reaction condition:298 K, 0.2 MPa, C2H6∶CO2=1∶1, 25 mg 1Pd-1Rh catalyst for recycling)
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