Homogeneous catalysis using supercritical fluids: Recent trends and systems studied

Jessop, Philip G.

doi:10.1016/j.supflu.2005.11.025

Cited by 124 publications

(47 citation statements)

References 237 publications

(105 reference statements)

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“…CO 2 + H 2 -HCOOH, DG 273 K = 32.9 kJ mol À1 (20) To shift the reaction equilibrium, it is necessary to add a base (inorganic or organic) to the reaction system. 260 With the addition of an inorganic base, formate is generated which subsequently needs strong acid to convert to formic acid.…”

Section: Synthesis Of Formic Acid and Formatesmentioning

confidence: 99%

“…6,11,12,14,16,17 To combine the desirable reactivity of homogeneous catalysts with the recyclability of heterogeneous catalysts, significant progress has been made in this direction, including the immobilization of homogeneous catalysts, exploitation of novel heterogeneous catalysts, and the use of green solvents such as ionic liquids (ILs) and supercritical CO 2 (scCO 2 ). [18][19][20] There have been several excellent reviews regarding CO 2 conversions as well as catalytic hydrogenation of CO 2 . 3,6,9,11,[14][15][16][21][22][23][24][25][26][27][28] However, these reviews primarily focus on general aspects of CO 2 applications and homogenously catalyzed hydrogenation of CO 2 .…”

Section: Introductionmentioning

confidence: 99%

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Recent advances in catalytic hydrogenation of carbon dioxide

et al. 2011

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Owing to the increasing emissions of carbon dioxide (CO 2 ), human life and the ecological environment have been affected by global warming and climate changes. To mitigate the concentration of CO 2 in the atmosphere various strategies have been implemented such as separation, storage, and utilization of CO 2 . Although it has been explored for many years, hydrogenation reaction, an important representative among chemical conversions of CO 2 , offers challenging opportunities for sustainable development in energy and the environment. Indeed, the hydrogenation of CO 2 not only reduces the increasing CO 2 buildup but also produces fuels and chemicals. In this critical review we discuss recent developments in this area, with emphases on catalytic reactivity, reactor innovation, and reaction mechanism. We also provide an overview regarding the challenges and opportunities for future research in the field (319 references).

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Section: Synthesis Of Formic Acid and Formatesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Recent advances in catalytic hydrogenation of carbon dioxide

et al. 2011

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“…Supercritical carbon dioxide (scCO 2 ) is an attractive alternative to conventional organic solvents, due to its environmentally benign, non-toxic, and non-flammable nature, complete miscibility with gases, adjustable dissolving power, and easy separation from liquid/solid products after reactions [1][2][3][4]. In addition, scCO 2 can have several advantages, which are the absence of gas-liquid mass transfer limitations, relatively high rates of molecular diffusion and heat transfer, and the possibility of molecular interactions with the dissolved reacting species (substrates or catalysts).…”

Section: Introductionmentioning

confidence: 99%

Selective hydrogenation of nitrostyrene to aminostyrene over Pt/TiO2 catalysts: Effects of pressurized carbon dioxide and catalyst preparation conditions

Fujita

Yoshida

Asai

et al. 2011

The Journal of Supercritical Fluids

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The present work has studied the influence of CO 2 pressurization on the hydrogenation of nitrostyrene (NS) using Pt/TiO 2 . With CO 2 pressurization up to 12 MPa (CO 2 -dissolved expanded liquid (CXL) phase), the over-all reaction rate and the selectivity to aminostyrene (AS) increased. At higher CO 2 pressures where all NB dissolved in scCO 2 (scCO 2 -homogeneous phase), both of them decreased with increasing the CO 2 pressure. The phase behavior was an important factor for the present reaction system. It was also found that the presence of pressurized CO 2 gave higher selectivity to AS than in its absence at any conversion level. This was ascribed to retardation effects of dense phase CO 2 on the hydrogenation of AS to ethylaniline. Competitive adsorption of nitro and vinyl groups was suggested to determine the product selectivity. FTIR measurements showed that the pressurized CO 2 lowers the reactivity of the nitro group, and this effect is stronger in scCO 2 -homogeneous phase than in CXL phase, resulting in the lower AS selectivity in the former phase. Lower Pt loadings and higher catalyst reduction temperatures gave Pt/TiO 2 catalysts more selective for the AS formation. FTIR measurements of adsorbed CO over the catalysts suggested that the presence of less-coordinated Pt atoms on edge, corner and kink sites was significant for the selective hydrogenation of NS to AS.

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“…14,15 The study of model reactions is an efficient strategy for acquiring knowledge of the chemical reactivity in sc-CO 2 , as is the case for the cyclocondensation reaction, which is an important and general route to the construction of five-membered heterocyclic ring systems. There are few examples devoted to cyclocondensation reactions using SCF as the reaction media; 16 the synthesis of pyrazoles, for example, has not yet been reported.…”

Section: Introductionmentioning

confidence: 99%

The effect of pressurized carbon dioxide on the cyclocondensation reaction between 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones and hydrazines

Rossatto¹,

Casanova²,

Lima³

et al. 2013

Arkivoc

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The synthesis of 1-unsubstituted and 1-phenyl-5-trifluoromethylpyrazoles from the reaction of 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones [CF 3 C(O)CH=C(R 1 )OR, where R = Me, Et and R 1 = H, Me, Ph] with hydrazines [NH 2 NHR 2 , where R 2 = H, Ph] in pressurized carbon dioxide is reported for the first time. Reaction conditions such as pressure, temperature and time were evaluated. The methodology developed herein was suitable to synthesize products in moderate to excellent yields (60 % -96 %) and short reaction times (15 -45 min).

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Homogeneous catalysis using supercritical fluids: Recent trends and systems studied

Cited by 124 publications

References 237 publications

Recent advances in catalytic hydrogenation of carbon dioxide

Recent advances in catalytic hydrogenation of carbon dioxide

Selective hydrogenation of nitrostyrene to aminostyrene over Pt/TiO2 catalysts: Effects of pressurized carbon dioxide and catalyst preparation conditions

The effect of pressurized carbon dioxide on the cyclocondensation reaction between 4-alkoxy-1,1,1-trifluoro-3-alken-2-ones and hydrazines

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