Jie Ke

Chemical reactions in supercritical carbon dioxide: from laboratory to commercial plantThis work was presented at the Green Solvents for Catalysis Meeting held in Bruchsal, Germany, 13–16th October 2002.

The application of supercritical carbon dioxide in continuous, fixed bed reactors has allowed the successful development of a variety of industrially viable synthetic transformations. The world’s first, multi-reaction, supercritical flow reactor was commissioned in 2002 as a direct result of the successful collaboration between the Clean Technology Group at the University of Nottingham and the fine chemicals manufacturer, Thomas Swan & Co. Ltd. We highlight the development of this project from laboratory to plant scale, particularly in the context of the hydrogenation of isophorone. Phase data for the system; isophorone + H2 + CO2, are presented for the first time. Overall, we present a progress report about an on-going Green Chemistry initiative that has successfully forged strong links between Industry and Academia.

Electrodeposition of metals from supercritical fluids

Electrodeposition is a widely used materials-deposition technology with a number of unique features, in particular, the efficient use of starting materials, conformal, and directed coating. The properties of the solvent medium for electrodeposition are critical to the techniques applicability. Supercritical fluids are unique solvents which give a wide range of advantages for chemistry in general, and materials processing in particular. However, a widely applicable approach to electrodeposition from supercritical fluids has not yet been developed. We present here a method that allows electrodeposition of a range of metals from supercritical carbon dioxide, using acetonitrile as a co-solvent and supercritical difluoromethane. This method is based on a careful selection of reagent and supporting electrolyte. There are no obvious barriers preventing this method being applied to deposit a range of materials from many different supercritical fluids. We present the deposition of 3-nm diameter nanowires in mesoporous silica templates using this methodology.

Maximising opportunities in supercritical chemistry: the continuous conversion of levulinic acid to γ-valerolactone in CO2

Phase behaviour is manipulated during the hydrogenation of aqueous levulinic acid in supercritical CO(2) to separate almost pure gamma-valerolactone from water and unreacted acid with reduced energy requirements compared to conventional processing.

Electrodeposition from supercritical fluids

Recent studies have shown that it is possible to electrodeposit a range of materials, such as Cu, Ag and Ge, from various supercritical fluids, including hydrofluorocarbons and mixtures of CO2 with suitable co-solvents. In this perspective we discuss the relatively new field of electrodeposition from supercritical fluids. The perspective focuses on some of the underlying physical chemistry and covers both practical and scientific aspects of electrodeposition from supercritical fluids. We also discuss possible applications for supercritical fluid electrodeposition and suggest some key developments that are required to take the field to the next stage.

The fibre optic reflectometer: A new and simple probe for refractive index and phase separation measurements in gases, liquids and supercritical fluids

A fibre optic reflectometer (FOR) has been developed to monitor refractive index (n) and density (ρ) changes in gases, liquids and supercritical fluids (SCFs). The key operating principle is the measurement of the intensity of light from a light emitting diode, LED, which is reflected from the end of a fibre immersed in the medium. The amount of reflected light depends on the difference between the refractive indices of the fibre and the medium. The refractive index of the medium is related in turn to its density. The FOR is particularly sensitive to phase separation, a key aspect of supercritical fluid systems, because of the density discontinuity which accompanies the separation. This device allows the collection of data with a high spatial (9 μm-fibre diameter) and time (∼0.02 s) resolution. The small size of the fibre optic probe means that it can be put into operating reactors and even catalyst beds. Experiments are described with pure CO2 and CHF3, and mixtures CO2 + cyclohexane and CO2 + MeOH over wide pressure and temperatures ranges. The measurements are in excellent agreement with published data for these systems.

The Electrodeposition of Silver from Supercritical Carbon Dioxide/Acetonitrile

Cyclic voltammetry of silver coordination complexes in acetonitrile and in a single-phase supercritical carbon dioxide/acetonitrile (scCO2/CH3CN) system is reported. Five silver precursors are investigated: (1,5-cyclooctadiene)(hexafluoroacetylacetonato) silver(I) [Ag(hfac)(COD)], (hexafluoroacetylacetonato)(triphenylphosphine) silver(I) [Ag(hfac)(PPh3)], (perfluorooctanoato)bis(triphenylphosphine) silver(I) [Ag(CF3(CF2)6CO2)(PPh3)2], tetrakis(triphenylphosphine) silver(I) tetrafluoroborate [Ag(PPh3)4][BF4] and tetrakis(acetonitrile) silver(I) tetrafluoroborate [Ag(CH3CN)4][BF4]. Of these, [Ag(CH3CN)4][BF4] is found to be the most suitable for electrodeposition of silver from scCO2/CH3CN.

Acoustic measurements of critical points for four-component mixtures in hydroformylation reactions in carbon dioxide

Abstract A simple acoustic technique has been used to study the vapour–liquid critical points of the reaction mixtures of hydroformylation in carbon dioxide. The systems CO2+CO+H2+propene and CO2+CO+H2+hex-1-ene have been investigated. These two quaternary systems were measured by the pseudo-binary approach (i.e. the ratio of alkene, CO and H2 being held constant). The effects of the solutes (alkene, CO and H2) on the critical points in the CO2-rich fluids are discussed.

Detecting phase transitions in supercritical mixtures: an enabling tool for greener chemical reactions

Detecting phase transitions in high-pressure CO2 and supercritical fluids was first attempted in the nineteenth century. By contrast, Green Chemistry, the design and implementation of cleaner methods of manufacturing and processing chemicals, is barely 20 years old. Now, the use of CO2 as an environmentally more acceptable replacement for traditional solvents for greener chemical reactions is creating the need for new, more rapid methods for elucidating high-pressure phase behaviour. This paper describes the advantages and limitations of a number of approaches, developed in Nottingham, to meet this need, including acoustic measurements, shear-mode quartz sensors, the fibre-optic reflectometer, the use of holey fibres, attenuated total reflectance infrared spectroscopy and pressure drop measurements.

A Versatile Precursor System for Supercritical Fluid Electrodeposition of Main-Group Materials.

For the first time, a versatile electrolyte bath is described that can be used to electrodeposit a wide range of p-block elements from supercritical difluoromethane (scCH2 F2 ). The bath comprises the tetrabutylammonium chlorometallate complex of the element in an electrolyte of 50×10(-3)  mol dm(-3) tetrabutylammonium chloride at 17.2 MPa and 358 K. Through the use of anionic ([GaCl4 ](-) , [InCl4 ](-) , [GeCl3 ](-) , [SnCl3 ](-) , [SbCl4 ](-) , and [BiCl4 ](-) ) and dianionic ([SeCl6 ](2-) and [TeCl6 ](2-) ) chlorometallate salts, the deposition of elemental Ga, In, Ge, Sn, Sb, Bi, Se, and Te is demonstrated. In all cases, with the exception of gallium, which is a liquid under the deposition conditions, the resulting deposits are characterised by SEM, energy-dispersive X-ray analysis, XRD and Raman spectroscopy. An advantage of this electrolyte system is that the reagents are all crystalline solids, reasonably easy to handle and not highly water or oxygen sensitive. The results presented herein significantly broaden the range of materials accessible by electrodeposition from supercritical fluid and open up the future possibility of utilising the full scope of these unique fluids to electrodeposit functional binary or ternary alloys and compounds of these elements.

New design of fiber-optic reflectometer for determining the phase boundary of multicomponent fluid mixtures at high pressures and high temperatures

A dynamic synthetic method based on an optic fiber sensor has been developed to measure phase boundaries of multicomponent fluid at high temperatures >300°C and pressures >30MPa. The breakthrough has been the design of the equilibrium cell containing the optic fiber, which gives highly reproducible signals for the phase transition. We demonstrate that this method can clearly distinguish between dew points and bubble points in the phase transitions of mixtures. Overall, the method is characterized by speed, simplicity, high pressures, and high temperatures.