Enhanced stability of highly-dispersed copper catalyst supported by hierarchically porous carbon for long term selective hydrogenation

Hu, Naibo; Li, Xiao yun; Liu, Si Ming; Wang, Zhao; He, Xiao Ke; Hou, Yue; Wang, Yu Xiang; Deng, Zhao; Chen, Li Hua; Su, Bao‐Lian

doi:10.1016/s1872-2067(20)63570-7

Cited by 26 publications

(13 citation statements)

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“…Our Cu/SiO 2 systems also outperform Pd-based NPs (generally >1% propene conversion, same conditions), single-atom Pd and Pt/Cu (∼0.1 and ∼1% propene conversion; corresponding gas feed: 1.9/2% butadiene, 70/20% propene, 4.7/16% hydrogen and balance He, respectively), , Au/SiO 2 catalysts (for which the conversion of propene was already particularly low, <0.1%, same conditions), , or PdAu bimetallic nanorods (selectivity to butenes below 90%, same conditions) . To the best of our knowledge the highest butenes selectivity (>98%) under similar conditions was reported for Cu-based catalysts obtained via carbonization of MOFs (HKUST-1, 50 wt % Cu) …”

Section: Results and Discussionmentioning

confidence: 62%

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Supported Cu Nanoparticles as Selective and Stable Catalysts for the Gas Phase Hydrogenation of 1,3-Butadiene in Alkene-Rich Feeds

et al. 2020

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Supported copper nanoparticles are a promising alternative to supported noble metal catalysts, in particular for the selective gas phase hydrogenation of polyunsaturated molecules. In this article, the catalytic performance of copper nanoparticles (3 and 7 nm) supported on either silica gel or graphitic carbon is discussed in the selective hydrogenation of 1,3-butadiene in the presence of a 100-fold excess of propene. We demonstrate that the routinely used temperature ramp-up method is not suitable in this case to reliably measure catalyst activity, and we present an alternative measurement method. The catalysts exhibited selectivity to butenes as high as 99% at nearly complete 1,3-butadiene conversion (95%). Kinetic analysis showed that the high selectivity can be explained by considering H 2 activation as the rate-limiting step and the occurrence of a strong adsorption of 1,3-butadiene with respect to mono-olefins on the Cu surface. The 7 nm Cu nanoparticles on SiO 2 were found to be a very stable catalyst, with almost full retention of its initial activity over 60 h of time on stream at 140 °C. This remarkable long-term stability and high selectivity toward alkenes indicate that Cu nanoparticles are a promising alternative to replace precious-metal-based catalysts in selective hydrogenation.

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Section: Results and Discussionmentioning

confidence: 62%

“… 54 To the best of our knowledge the highest butenes selectivity (>98%) under similar conditions was reported for Cu-based catalysts obtained via carbonization of MOFs (HKUST-1, 50 wt % Cu). 57 …”

Section: Results and Discussionmentioning

confidence: 99%

Supported Cu Nanoparticles as Selective and Stable Catalysts for the Gas Phase Hydrogenation of 1,3-Butadiene in Alkene-Rich Feeds

et al. 2020

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“…[9] 1,3-BD can be selectively hydrogenated to butenes (such as 1-butene, trans-2-butene, and cis-2-butene), which improves carbon utilization. [10] However, these butenes can easily be further hydrogenated to butane due to the low barrier to this reaction. [11] Hence, improving butene selectivity is one of the most crucial factors for developing 1,3-BD hydrogenation catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…Currently, one of the most widely utilized approaches for increasing butene selectivity is the addition of a second metal element to single-metal materials to produce bimetallic catalysts. [9,10] This second metal can influence the surface structure and electronic properties of the metals, enhance the hydrogen adsorption ability of the catalyst, and decrease butene adsorption. [9] Therefore, catalyst activity and butene selectivity can be enhanced.…”

Section: Introductionmentioning

confidence: 99%

MIL‐100(Fe) Supported Pt−Co Nanoparticles as Active and Selective Heterogeneous Catalysts for Hydrogenation of 1,3‐Butadiene

Liu

Han

et al. 2022

ChemistryOpen

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Superior catalytic performance for selective 1,3‐butadiene (1,3‐BD) hydrogenation can usually be achieved with supported bimetallic catalysts. In this work, Pt−Co nanoparticles and Pt nanoparticles supported on metal–organic framework MIL‐100(Fe) catalysts (MIL=Materials of Institut Lavoisier, PtCo/MIL‐100(Fe) and Pt/MIL‐100(Fe)) were synthesized via a simple impregnation reduction method, and their catalytic performance was investigated for the hydrogenation of 1,3‐BD. Pt1Co1/MIL‐100(Fe) presented better catalytic performance than Pt/MIL‐100(Fe), with significantly enhanced total butene selectivity. Moreover, the secondary hydrogenation of butenes was effectively inhibited after doping with Co. The Pt1Co1/MIL‐100(Fe) catalyst displayed good stability in the 1,3‐BD hydrogenation reaction. No significant catalyst deactivation was observed during 9 h of hydrogenation, but its catalytic activity gradually reduces for the next 17 h. Carbon deposition on Pt1Co1/MIL‐100(Fe) is the reason for its deactivation in 1,3‐BD hydrogenation reaction. The spent Pt1Co1/MIL‐100(Fe) catalyst could be regenerated at 200 °C, and regenerated catalysts displayed the similar 1,3‐BD conversion and butene selectivity with fresh catalysts. Moreover, the rate‐determining step of this reaction was hydrogen dissociation. The outstanding activity and total butene selectivity of the Pt1Co1/MIL‐100(Fe) catalyst illustrate that Pt−Co bimetallic catalysts are an ideal alternative for replacing mono‐noble‐metal‐based catalysts in selective 1,3‐BD hydrogenation reactions.

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“…Moreover, they found the pore size in catalysts had a significant effect on the mass transportation of dimethyl adipate reactants and could limit the hydrogenation reaction. We have recently synthesized monometallic Cu supported by hierarchically porous carbon (HPC) with a Cu loading as high as 40-50 wt% by the in situ carbonization of HKUST-1 (with a surface area of 1599 m 2 g −1 ) at a high temperature (>400 • C) [36]. The special macro-mesoporous structure of the carbon support with well-confined Cu nanoparticles in Cu/HPC provided a rather high catalytic performance-i.e., butadiene conversion stayed at 100% for over 120 h of time on stream-showing that combining a porous hierarchy with a high surface area is an efficient way to improve the catalytic stability of mono-metallic Cu catalyst.…”

Section: Introductionmentioning

confidence: 99%

Highly Enhanced Catalytic Stability of Copper by the Synergistic Effect of Porous Hierarchy and Alloying for Selective Hydrogenation Reaction

Yuan

Wang

Jin³

et al. 2021

Catalysts

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Supported copper has a great potential for replacing the commercial palladium-based catalysts in the field of selective alkynes/alkadienes hydrogenation due to its excellent alkene selectivity and relatively high activity. However, fatally, it has a low catalytic stability owing to the rapid oligomerization of alkenes on the copper surface. In this study, 2.5 wt% Cu catalysts with various Cu:Zn ratios and supported on hierarchically porous alumina (HA) were designed and synthesized by deposition–precipitation with urea. Macropores (with diameters of 1 μm) and mesopores (with diameters of 3.5 nm) were introduced by the hydrolysis of metal alkoxides. After in situ activation at 350 °C, the catalytic stability of Cu was highly enhanced, with a limited effect on the catalytic activity and alkene selectivity. The time needed for losing 10% butadiene conversion for Cu1Zn3/HA was ~40 h, which is 20 times higher than that found for Cu/HA (~2 h), and 160 times higher than that found for Cu/bulky alumina (0.25 h). It was found that this type of enhancement in catalytic stability was mainly due to the rapid mass transportation in hierarchically porous structure (i.e., four times higher than that in bulky commercial alumina) and the well-dispersed copper active site modified by Zn, with identification by STEM–HAADF coupled with EDX. This study offers a universal way to optimize the catalytic stability of selective hydrogenation reactions.

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Enhanced stability of highly-dispersed copper catalyst supported by hierarchically porous carbon for long term selective hydrogenation

Cited by 26 publications

References 50 publications

Supported Cu Nanoparticles as Selective and Stable Catalysts for the Gas Phase Hydrogenation of 1,3-Butadiene in Alkene-Rich Feeds

Supported Cu Nanoparticles as Selective and Stable Catalysts for the Gas Phase Hydrogenation of 1,3-Butadiene in Alkene-Rich Feeds

MIL‐100(Fe) Supported Pt−Co Nanoparticles as Active and Selective Heterogeneous Catalysts for Hydrogenation of 1,3‐Butadiene

Highly Enhanced Catalytic Stability of Copper by the Synergistic Effect of Porous Hierarchy and Alloying for Selective Hydrogenation Reaction

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