Study on the photocatalytic oxidative dehydrogenation of ethane with CO2 over Pd-Rh /TiO2 catalyst

doi:10.11949/0438-1157.20200172

Abstract

Abstract:

Pd-Rh/ TiO₂ catalyst was prepared by impregnation reduction method for photocatalytic CO₂oxidative dehydrogenation of ethane to C₂H₄ at room temperature. Effects of different Pd/Rh ratio of the catalysts on the photocatalytic performances were studied. Morphology characteristics of the catalysts were examined by XRD, EDX-mapping, TEM, HRTEM and XPS. The photocatalytic performances of the catalysts were measured by UV-Vis and PL. The mechanism of oxidative dehydrogenation of ethane was examined with in situ FTIR. The internal electrons transfer between Pd cluster and Rh cluster effectively improves the photocatalytic performance. It reduces the electron density of the Pd surface, and promotes the separation of e^- and h⁺. It also improves the adsorption of C₂H₄ and CO₂ on the surface of the catalyst. The contrast experiments of CO₂ and Ar prove that CO₂ does help to eliminate carbon deposed on the catalyst and to promote ethylene generating with itself reduced by H₂.

Key words: catalysis, alkane, carbon dioxide, oxidation, dehydrogenation, titanium dioxide, palladium, rhodium

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。

关键词: 催化, 烷烃, 二氧化碳, 氧化, 脱氢, 二氧化钛, 钯, 铑

CLC Number:

TQ 116.2⁺5

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.

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.

Figures/Tables 8

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)
催化剂	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

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
催化剂^①	Pd负载量^②/ %(质量)	Rh负载量^②/ %(质量)	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	—	—	—

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)

Fig.2 XRD, SEM, HRTEM, EDX-mapping patterns of different metal ratio of Pd-Rh/TiO2

Fig.3 Survey spectra of Pd, 1Pd -1Rh and Rh samples and XPS spectra of Pd 3d and Rh 3d

Fig.4 Optical properties of Pd-Rh/TiO2 with different metal proportions

Fig.5 In stiu FTIR spectra of photocatalytic oxidation of ethane for dehydrogenation reaction with 1Pd-1Rh

Fig.6 Mechanism of dehydrogenation of ethane oxidized by CO2 catalyzed by Pd-Rh bimetal photocatalyst

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Study on the photocatalytic oxidative dehydrogenation of ethane with CO₂ over Pd-Rh /TiO₂ catalyst

Pd-Rh/TiO₂光催化CO₂氧化乙烷脱氢研究

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