The Role of Copper Speciation in the Low Temperature Oxidative Upgrading of Short Chain Alkanes over Cu/ZSM‐5 Catalysts

Armstrong, Robert D.; Peneau, Virginie; Ritterskamp, Nadine; Kiely, Christopher J.; Taylor, Stuart Hamilton; Hutchings, Graham J.

doi:10.1002/cphc.201701046

Cited by 24 publications

(17 citation statements)

References 74 publications

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“…Of course, as well as using novel materials, we can consider new ways of making Cu‐based catalysts. One approach, which could be environmentally beneficial is to avoid a solvent in the preparation and we have recently reported data for such a catalyst produced by anti‐solvent methods utilising supercritical CO 2 or gas phase chemical vapour impregnation (CVI) . This produces good catalysts with high dispersion of the Cu, but for efficiency, the former requires excellent recycling of the CO 2 .…”

Section: Novel Catalystsmentioning

confidence: 99%

Methanol Synthesis from CO₂ Hydrogenation

2019

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In the future we will be phasing out the use of fossil fuels in favour of more sustainable forms of energy, especially solar derived forms such as hydroelectric, wind and photovoltaic. However, due to the variable nature of the latter sources which depend on time of day, and season of the year, we also need to have a way of storing such energy at peak production times for use in times of low production. One way to do this is to convert such energy into chemical energy, and the principal way considered at present is the production of hydrogen. Although this may be achieved directly in the future via photocatalytic water splitting, at present it is electrolytic production which dominates thinking. In turn, it may well be important to store this hydrogen in an energy dense liquid form such as methanol or ammonia. In this brief review it is emphasised that CO2 is the microscopic carbon source for current industrial methanol synthesis, operating through the surface formate intermediate, although when using CO in the feed, it is CO which is hydrogenated at the global scale. However, methanol can be produced from pure CO2 and hydrogen using conventional and novel types of catalysts. Examples of such processes, and of a demonstrator plant in construction, are given, which utilize CO2 (which would otherwise enter the atmosphere directly) and hydrogen which can be produced in a sustainable manner. This is a fast‐evolving area of science and new ideas and processes will be developed in the near future.

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Section: Novel Catalystsmentioning

confidence: 99%

Methanol Synthesis from CO₂ Hydrogenation

2019

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“…The oxidation of C 1 -C 3 alkanes utilising H 2 O 2 in conjunction with HZSM-5 [28][29][30][31][32] in addition to AuPd nanoparticles supported on TiO 2 [33,34] at low temperature have been extensively reported, with the valorisation of methane to methanol in particular an attractive option to produce a versatile chemical feedstock. Indeed, we have previously reported that greater selectivity, at comparable catalytic productivity, towards methane can be achieved when generating H 2 O 2 from H 2 and O 2 compared to preformed, commercially synthesised H 2 O 2 [35].…”

Section: Introductionmentioning

confidence: 99%

The Direct Synthesis of H2O2 and Selective Oxidation of Methane to Methanol Using HZSM-5 Supported AuPd Catalysts

et al. 2019

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In this study we show that using gold palladium nanoparticles supported on a commercial aluminosilicate (HZSM-5) prepared using a wet co-impregnation method it is possible to produce hydrogen peroxide from molecular H 2 and O 2 via the direct synthesis reaction. Furthermore, we investigate the efficacy of these catalysts towards the oxidation of methane to methanol using commercially available H 2 O 2. The effect of SiO 2 : Al 2 O 3 ratio and calcination temperature is evaluated and a direct correlation between support acidity and the catalytic activity towards H 2 O 2 synthesis and methanol production is observed.

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“…This TOF is still significantly higher than the previously reported results. 34,48,49,75,87,88 Despite the existence of the bottleneck due to the activity-selectivity trade-off, it is still promising to improve DMTM catalysts using H2O2 as the oxidant in the future.…”

Section: Kinetic Analysismentioning

confidence: 99%

“…47 Hutchings and his colleagues found that copper addition in Cu-ZSM-5 can provide up to 97 % CH3OH selectivity in the presence of H2O2 at 50°C. 48 Tang et al reported that Cu1-O4/ZSM-5 single atom catalyst exhibits a 99% selectivity of C1 oxide with high conversion of CH4 at 50 °C. 49 However, H2O2 is likely to readily generate the free radicals of •OH and •OOH as well, thereby possibly triggering a Fenton reaction and reducing the CH3OH selectivity.…”

Section: Introductionmentioning

confidence: 99%

Advantages and Limitations of Hydrogen Peroxide for Direct Oxidation of Methane to Methanol at Mono-Copper Active Sites in Cu-Exchanged Zeolites

Cheng

Chen

et al. 2022

Preprint

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The oxidant is a crucial factor affecting the performance of direct oxidation of methane to methanol (DMTM). It is still extremely challenging to realize one-pot DMTM using dioxygen. So far, hydrogen peroxide is still the most frequently reported green oxidant for DMTM with high selectivity of methanol. Aiming to achieve insights into the influence of oxidants on the DMTM performance and to improve catalysts, we computationally investigated the reaction mechanisms of DMTM using hydrogen peroxide at mono-copper sites in three kinds of Cu-exchanged zeolites with different sizes of the micropores. We identified the common advantage and limitations of hydrogen peroxide as the oxidant. In contrast to molecular oxygen, the O-O bond of hydrogen peroxide could be easily broken to produce reactive surface oxygen species, enabling the facile C-H bond activation of methane at a lower temperature. However, the radical-like mechanism for the C-H bond activation in DMTM using hydrogen peroxide makes the C-H bond breaking of methanol ineluctably superior to methane. This leads to the inevitable trade-off between selectivity and activity for DMTM. Moreover, the lower O-H bonding energy of hydrogen peroxide would also result in the significant self-decomposition of hydrogen peroxide. Despite the existence of these bottlenecks, the kinetic analysis manifests that it is still promising to improve catalysts to boost the performance of DMTM using hydrogen peroxide.

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The Role of Copper Speciation in the Low Temperature Oxidative Upgrading of Short Chain Alkanes over Cu/ZSM‐5 Catalysts

Cited by 24 publications

References 74 publications

Methanol Synthesis from CO₂ Hydrogenation

Methanol Synthesis from CO₂ Hydrogenation

The Direct Synthesis of H2O2 and Selective Oxidation of Methane to Methanol Using HZSM-5 Supported AuPd Catalysts

Advantages and Limitations of Hydrogen Peroxide for Direct Oxidation of Methane to Methanol at Mono-Copper Active Sites in Cu-Exchanged Zeolites

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The Role of Copper Speciation in the Low Temperature Oxidative Upgrading of Short Chain Alkanes over Cu/ZSM‐5 Catalysts

Cited by 24 publications

References 74 publications

Methanol Synthesis from CO2 Hydrogenation

Methanol Synthesis from CO2 Hydrogenation

The Direct Synthesis of H2O2 and Selective Oxidation of Methane to Methanol Using HZSM-5 Supported AuPd Catalysts

Advantages and Limitations of Hydrogen Peroxide for Direct Oxidation of Methane to Methanol at Mono-Copper Active Sites in Cu-Exchanged Zeolites

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Methanol Synthesis from CO₂ Hydrogenation

Methanol Synthesis from CO₂ Hydrogenation