Electronic effects on the catalytic disproportionation of formic acid to methanol by [Cp*Ir<sup>III</sup>(R-bpy)Cl]Cl complexes

Sasayama, Alissa F.; Moore, Curtis E.; Kubiak, Clifford P.

doi:10.1039/c5dt04606h

Cited by 22 publications

(25 citation statements)

References 13 publications

(21 reference statements)

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“…The result is in contrast to the reported homogeneous catalytic systems based on similar Ir complexes. 20,[23][24]29 In our heterogeneous system, free bipyridine ligands initiate the dehydrogenation of HCO2H at a faster rate in the absence of H2 and therefore H2 pressure was necessary for the production of methanol. Increase in temperature showed higher HCO2H conversion whereas the methanol selectivity started to decrease (Figure 3c).…”

Section: Resultsmentioning

confidence: 92%

“…Typically, homogeneous catalysts were explored for the conversion of formic acid, among which iridium-based complexes produced the most promising results. 20,[22][23][24]29 Here we report the first example of a heterogeneous catalyst, based on [Cp*Ir(H 2 O) 3 ]SO 4 , for the hydrogenation of formic acid to methanol. We used a robust support for the immobilization of the [Cp*Ir(H 2 O) 3 ]SO 4 complex to achieve a heterogeneous catalyst, where the active catalytic centers keep their identity upon heterogenization.…”

Section: ■ Introductionmentioning

confidence: 99%

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Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst

Gevers

Emwas

et al. 2019

ACS Sustainable Chem. Eng.

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Although the conversion of carbon dioxide (and its derivatives) into methanol has attracted remarkable attention in the last two decades, performing this process over a heterogeneous catalyst under mild conditions is still a challenging task. We report bipyridine-functionalized iridium-based heterogeneous catalysts for the hydrogenation of formic acid to produce methanol at low temperature. The solid catalysts were obtained by post-synthetic metalation of bipyridine-functionalized organosilica nanotubes with a [Cp*Ir(H2O)3]SO4 (Cp* = η 5-pentamethylcyclopentadienyl) complex. Detailed studies including N2 adsorption, TEM, XPS, and 13 C CP MAS NMR confirmed the stable structures of nanotube supports and the molecular nature of the active species. The catalysts showed competitive methanol selectivities compared to their homogeneous counterpart under similar reaction conditions. Addition of strong acids (such as triflic acid) showed improved methanol selectivity, whereas the presence of free bipyridine groups was found to promote the dehydrogenation of formic acid, resulting in low methanol selectivity. The catalyst showed excellent reusability over four consecutive cycles without any significant loss in activity and maintained its heterogeneous nature in extremely high acidic environment.

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Section: Resultsmentioning

confidence: 92%

Section: ■ Introductionmentioning

confidence: 99%

Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst

Gevers

Emwas

et al. 2019

ACS Sustainable Chem. Eng.

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“… 397 In 2016, the Kubiak group demonstrated the electronic effects on the catalytic disproportionation of HCOOH to CH 3 OH using cationic iridium bipyridine complexes ( Ir15 , Ir16 ) and noticed that the unsubstituted bipyridine complex and the 4- t Bu substituted complex exhibited the highest selectivity toward methanol. 398 Soon after, Laurenczy and Himeda reported their study on various iridium catalysts with substituted 2,2′-bipyridine derivatives for disproportionation of formic acid. Their report revealed that the iridium catalyst bearing 5,5′-dimethyl-2,2′- bipyridine ( Ir14a ) showed high TON and selectivity toward methanol.…”

Section: Methanol Economymentioning

confidence: 99%

Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics

2021

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As the world pledges to significantly cut carbon emissions, the demand for sustainable and clean energy has now become more important than ever. This includes both production and storage of energy carriers, a majority of which involve catalytic reactions. This article reviews recent developments of homogeneous catalysts in emerging applications of sustainable energy. The most important focus has been on hydrogen storage as several efficient homogeneous catalysts have been reported recently for (de)hydrogenative transformations promising to the hydrogen economy. Another direction that has been extensively covered in this review is that of the methanol economy. Homogeneous catalysts investigated for the production of methanol from CO 2 , CO, and HCOOH have been discussed in detail. Moreover, catalytic processes for the production of conventional fuels (higher alkanes such as diesel, wax) from biomass or lower alkanes have also been discussed. A section has also been dedicated to the production of ethylene glycol from CO and H 2 using homogeneous catalysts. Well-defined transition metal complexes, in particular, pincer complexes, have been discussed in more detail due to their high activity and well-studied mechanisms.

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“…A variety of [Cp*Ir III (R-bpy)Cl] Cl (R-bpy = 4,4'-di-R-2,2'-bipyridine; R = CF 3 , H, Me, tBu, OMe) complexes was synthesized by Kubiak and co-workers to study the same reaction ( Figure 6), finding that the unsubstituted (R = H) complex exhibited the highest selectivity to methanol (< 2 %). [66] Acidic conditions were favorable for the hydrogenation of formic acid into methanol. The addition of H 2 SO 4 led to methanol selectivity of up to 47.1 % after the hydrogenation of formic acid at 4.5 MPa of H 2 and 50-60°C using an Ir complex bearing 5,5'-dimethyl-2,2'-bipyridine.…”

Section: Ir-based Catalystsmentioning

confidence: 99%

CO₂ Reduction to Methanol in the Liquid Phase: A Review

et al. 2020

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Excessive carbon dioxide (CO2) emissions have been subject to extensive attention globally, since an enhanced greenhouse effect (global warming) owing to a high CO2 concentration in the atmosphere could lead to severe climate change. The use of solar energy and other renewable energy to produce low‐cost hydrogen, which is used to reduce CO2 to produce bulk chemicals such as methanol, is a sustainable strategy for reducing carbon dioxide emissions and carbon resources. CO2 conversion into methanol is exothermic, so that low temperature and high pressure are favorable for methanol formation. CO2 is usually captured and recovered in the liquid phase. Herein, the emerging technologies for the hydrogenation of CO2 to methanol in the condensed phase are reviewed. The development of homogeneous and heterogeneous catalysts for this important hydrogenation reaction is summarized. Finally, mechanistic insight on CO2’s conversion into methanol over different catalysts is discussed by taking the available reaction pathways into account.

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Electronic effects on the catalytic disproportionation of formic acid to methanol by [Cp*Ir^III(R-bpy)Cl]Cl complexes

Cited by 22 publications

References 13 publications

Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst

Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst

Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics

CO₂ Reduction to Methanol in the Liquid Phase: A Review

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Electronic effects on the catalytic disproportionation of formic acid to methanol by [Cp*IrIII(R-bpy)Cl]Cl complexes

Cited by 22 publications

References 13 publications

Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst

Conversion of Formic Acid into Methanol Using a Bipyridine-Functionalized Molecular Heterogeneous Catalyst

Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics

CO2 Reduction to Methanol in the Liquid Phase: A Review

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Electronic effects on the catalytic disproportionation of formic acid to methanol by [Cp*Ir^III(R-bpy)Cl]Cl complexes

CO₂ Reduction to Methanol in the Liquid Phase: A Review