Ni stabilised on inorganic complex structures: superior catalysts for chemical CO2 recycling via dry reforming of methane

Saché, Estelle le; Pastor‐Pérez, Laura; Watson, David J.; Sepúlveda-Escribano, A.; Reina, Tomás Ramírez

doi:10.1016/j.apcatb.2018.05.051

Cited by 148 publications

(77 citation statements)

References 52 publications

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“…Moreover, the H 2 in syngas also decreased at CO 2 /ethanol higher than 1.4, while CO increased. This trend showcases the direct impact of the reversed WGSR during the dry reforming processes as reported elsewhere [23][24][25].…”

Section: Dry Reforming Of Ethanolsupporting

confidence: 87%

Dry Reforming of Ethanol and Glycerol: Mini-Review

Odriozola

Reina

2019

Catalysts

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Dry reforming of ethanol and glycerol using CO2 are promising technologies for H2 production while mitigating CO2 emission. Current studies mainly focused on steam reforming technology, while dry reforming has been typically less studied. Nevertheless, the urgent problem of CO2 emissions directly linked to global warming has sparked a renewed interest on the catalysis community to pursue dry reforming routes. Indeed, dry reforming represents a straightforward route to utilize CO2 while producing added value products such as syngas or hydrogen. In the absence of catalysts, the direct decomposition for H2 production is less efficient. In this mini-review, ethanol and glycerol dry reforming processes have been discussed including their mechanistic aspects and strategies for catalysts successful design. The effect of support and promoters is addressed for better elucidating the catalytic mechanism of dry reforming of ethanol and glycerol. Activity and stability of state-of-the-art catalysts are comprehensively discussed in this review along with challenges and future opportunities to further develop the dry reforming routes as viable CO2 utilization alternatives.

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Section: Dry Reforming Of Ethanolsupporting

confidence: 87%

Dry Reforming of Ethanol and Glycerol: Mini-Review

Odriozola

Reina

2019

Catalysts

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“…The reason for the very good resistance to carbon deposition for the aforementioned catalyst might be partly due to the formed La2O3 layer, within which the Ni metallic active sites are well dispersed and less prone to carbon accumulation. As recently reported [51], the Ce0.8Pr0.2O2-δsupported Ni catalyst prepared by the citrate sol-gel method, due to the presence of mobile active oxygen species in the Ce0.8Pr0.2O2-δ support, largely participates in the carbon removal via gasification to CO(g). Moreover, Ni particles smaller in size can reduce carbon accumulation [52].…”

Section: Characterization Of Used Catalystsmentioning

confidence: 55%

Encapsulated Ni@La2O3/SiO2 Catalyst with a One-Pot Method for the Dry Reforming of Methane

Wang

Liu

et al. 2019

Catalysts

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Ni nanoparticles encapsulated within La 2 O 3 porous system (Ni@La 2 O 3 ), the latter supported on SiO 2 (Ni@La 2 O 3 )/SiO 2 ), effectively inhibit carbon deposition for the dry reforming of methane. In this study, Ni@La 2 O 3 /SiO 2 catalyst was prepared using a one-pot colloidal solution combustion method. Catalyst characterization demonstrates that the amorphous La 2 O 3 layer was coated on SiO 2 , and small Ni nanoparticles were encapsulated within the layer of amorphous La 2 O 3 . During 50 h of dry reforming of methane at 700 • C and using a weight hourly space velocity (WHSV) of 120,000 mL g cat −1 h −1 , the CH 4 conversion obtained was maintained at 80%, which is near the equilibrium value, while that of impregnated Ni-La 2 O 3 /SiO 2 catalyst decreased from 63% to 49%. The Ni@La 2 O 3 /SiO 2 catalyst exhibited very good resistance to carbon deposition, and only 1.6 wt% carbon was formed on the Ni@La 2 O 3 /SiO 2 catalyst after 50 h of reaction, far lower than that of 11.5 wt% deposited on the Ni-La 2 O 3 /SiO 2 catalyst. This was mainly attributed to the encapsulated Ni nanoparticles in the amorphous La 2 O 3 layer. In addition, after reaction at 700 • C for 80 h with a high WHSV of 600,000 mL g cat −1 h −1 , the Ni@La 2 O 3 /SiO 2 catalyst exhibited high CH 4 conversion rate, ca. 10.10 mmol g Ni −1 s −1 . These findings outline a simple synthesis method to prepare supported encapsulated Ni within a metal oxide porous structure catalyst for the dry reforming of methane reaction.

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“…[27] It is worth adding that although the nickel nanoparticles reported here are not the smallest reported in the literature so far (the application of atomic layer deposition recently afforded nanoparticle size below 3 nm [56] ), this study demonstrates the potential of MOFs as sacrificial hosts for preparing highly dispersed nickel nanoparticles whose size is below those prepared by employing other type of oxides as stable nickel cation hosts, such as alkaline earth metal substituted MZr 1-x Ni x O 3 -δ perovskites [57] or the lanthanum zirconate pyrochlore La 2 Zr 2 À xNi x O 7 -δ. [58] Noteworthy, the use of MOF results in materials with a relatively high surface area (S. A. = 200 m 2 .g À 1 ) compared to that obtained with other types of purely inorganic sacrificial nickel host cited above (S.A. < 20 m 2 .g À 1 ), which can be seen as an additional benefit of this strategy in view catalysis applications.…”

Section: Catalysis Performancesmentioning

confidence: 95%

Porous Nickel‐Alumina Derived from Metal‐Organic Framework (MIL‐53): A New Approach to Achieve Active and Stable Catalysts in Methane Dry Reforming

et al. 2019

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An Al‐containing MIL‐53 metal‐organic framework with very high surface area (SBET=1130 m2.g−1, N2 sorption) was used as sacrificial template to prepare a nickel‐alumina‐based catalyst (Ni0AlMIL) highly active and stable in the reaction of dry reforming of methane (DRM). The procedure consisted in impregnating the activated (solvent free) MIL‐53 sample with a nickel precursor solution, then calcining the material to remove the organic linkers and subsequently reducing it to form the reduced nickel active phase. At the step of calcination, this procedure results in the formation of a porous uniform spinel phase with Ni nanospecies embedded in the alumina‐based matrix, as deduced from XRD, TPR and TEM analyses. This leads after reduction to a porous lamellar γ‐Al2O3 material with small Ni0 nanoparticles homogeneously dispersed and stabilized within the support. The performances of this catalyst in DRM are better than those of two reference Ni/alumina catalysts prepared for comparison by conventional nickel impregnation of two preformed alumina supports: a first one obtained by calcination of MIL‐53 (AlMIL) and a second one consisting of a commercial γ‐Al2O3 batch (AlCOM). Under steady state conditions at a temperature of 650 °C and a pressure of 1 bar, the higher CH4 and CO2 conversions (till 3 times higher than on Ni0/AlCOM), high catalytic stability (no loss of activity after 13–100 h) and higher selectivity towards DRM (H2:CO products ratio remaining at 1) on Ni0AlMIL compared to the other catalysts is believed to come from the particularly strong interaction between the nickel and alumina phases generated by using the unique high specific surface of the parent MOF support to deposit nickel. This creates an intimate mixing favorable to a persisting interaction of the nickel nanoparticles with the alumina support in the reduced material. The lamellar shape of the γ‐Al2O3 composing the catalyst and its remaining high specific surface may also contribute to the excellent Ni resistance to sintering and in turn to the inhibition of carbon nanotubes formation during the reaction.

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Ni stabilised on inorganic complex structures: superior catalysts for chemical CO2 recycling via dry reforming of methane

Cited by 148 publications

References 52 publications

Dry Reforming of Ethanol and Glycerol: Mini-Review

Dry Reforming of Ethanol and Glycerol: Mini-Review

Encapsulated Ni@La2O3/SiO2 Catalyst with a One-Pot Method for the Dry Reforming of Methane

Porous Nickel‐Alumina Derived from Metal‐Organic Framework (MIL‐53): A New Approach to Achieve Active and Stable Catalysts in Methane Dry Reforming

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