Cadmium sulfide preparation

The approach described later on in this chapter builds upon a report in 2002, in which we proposed microfluidic reactors as favourable systems for nanoparticle synthesis, and showed that nanocrystalline cadmium sulfide prepared in such reactors exhibited improved monodispersity compared with particles prepared in conventional bulk-scale vessels (Edel et al., 2002). 

Tsamouras, D. et al., Physicochemical characteristics of mixed copper-cadmium sulfides prepared by coprecipitation, Langmuir, 15, 8018, 1999. 

Cadmium Sulfide Photoconductor. CdS photoconductive films are prepared by both evaporation of bulk CdS and settHng of fine CdS powder from aqueous or organic suspension foUowed by sintering (60,61). The evaporated CdS is deposited to a thickness from 100 to 600 nm on ceramic substates. The evaporated films are polycrystaUine and are heated to 250°C in oxygen at low pressure to increase photosensitivity. Copper or silver may be diffused into the films to lower the resistivity and reduce contact rectification and noise. The copper acceptor energy level is within 0.1 eV of the valence band edge. Sulfide vacancies produce donor levels and cadmium vacancies produce deep acceptor levels. 

Elbaum R, Vega S, Hodes G (2001) Preparation and surface structure of nanocrystalline cadmium sulfide (sulfoselenide) precipitated from dimethyl sulfoxide solutions. Chem Mater 13(7) 2272-2280... 

Cadmium sulfide may be prepared by precipitation from an aqueous solution of its soluble salts such as cadmium chloride or cadmium nitrate by passing hydrogen sulfide. The reactions may he carried out in acidic, neutral or alkaline solutions using various cadmium salts to obtain different crystal modifications as shown in the table below. 

Cadmium sulfide also may be obtained by treatment of sodium or other alkali metal sulfide solution with that of a soluble cadmium salt. The compound also may be prepared by heating a mixture of cadmium or its oxide with sulfur at 800°C or by the reaction of H2S with cadmium vapor at 800°C. 

The manufactnring process for the important zinc and cadmium sulfide phosphors involves precipitation of the sulfide from purified salt solutions, e.g. the snlfate, with hydrogen snlfide. For ZnS Cu, the copper activator is added, as a readily decomposed derivative, to the sulfides and after grinding the components are fired in fnmaces at temperatures in the range 800-1200 °C. ZnS Ag, the bine phosphor nsed in CRTs, is prepared by firing zinc sulfide with silver nitrate at 1000 °C, nsnally in the presence of sodinm chloride to give the co-activating chloride ions. 

Dutta P, Fendler JH (2002) Preparation of cadmium sulfide nanoparticles in self-reproducing reversed micelles. J Colloid Interface Sci 247 47-53... 

Matijevic and Wilhelmy (I) prepared uniform spherical polycrystalline particles of cadmium sulfide (CdS) by reaction of Cd2+ ions with thioacetamide (TAA) in a dilute acidic media (pH < 2), as shown in the TEM and SEM images of Figure... 

Various materials have been synthetized in reverse micelles (3). Cadmium sulfide and cadmium selenide semiconductors (38-47) were the first materials prepared by this method. This has been extended to semiconductor alloys such as... 

The fluorescence of cadmium sulfide is strongly dependent on the particle size and the presence or absence of sulfide vacancies (57,58). The fluorescence of cadmium sulfide particles observed in solution in water (37,59,60) and in acetonitrile solution (59) is dependent on the particle method of preparation of CdS particles ... 

Sathaye, S. D. Patil, K. R. Paranjape, D. V. Mitra, A. Awate, S. V. Mandate, A. B. Preparation of Q-Cadmium Sulfide Ultrathin Films by a New Liquid-Liquid Interface Reaction Technique (LLRT). Langmuir2000, 16, 3487-3490,... 

There have been only a few reports of mesostructured metal sulfides. Mesoporous cadmium sulfide was prepared from polyethylene oxide surfactants and cadmium salts exposed to hydrogen sulfide [35], A study of the effects of the counter-anion on the formation of CdS mesostructures led to the conclusion that the use of cadmium nitrate and perchlorate salts improved the degree of order of the mesostructure over the chloride, sulfate and acetate salts. This effect was attributed to the stronger acidity of conjugate acid by-products of the reaction in the case of nitrates that leads to the dissolution of high-energy defects and enhances structural order. 

Early attempts to prepare low-melting alloys with cadmium sulfide (its natural form, greenockite, is orange-yellow) encouraged further investigation... 

By using polymer-controlled growth in ethylenediamine at 170°C, very long CdS nanowires (100px40 nm) were synthesized (Fig. 9a) [36]. Cadmium sulfide with different morphologies, such as nanoparticles and nanorods (Fig. 9b) [39], peanut-like nanostructures [37] and hollow nanospheres [38] (Fig. 9c) were prepared via solvothermal routes. 

Hydrazone cyclization and hydroalkylation [138-140] are rare examples of reactions conducted on a preparative scale, since the products were isolated in milligram amounts and not just identified in solution. As already mentioned in Section 6.2.5, photocorrosion of the semiconductor photocatalyst often prevents its use in preparative chemistry. This is very true also for colloidal semiconductors although the pseudo-homogeneous nature of their solutions allows one to conduct classical mechanistic investigations, until now they were too labile to be used in preparative chemistry [107, 141, 142]. In contrast to the above-mentioned reactions, in recent years we have isolated novel compounds on a gram-scale employing photostable zinc and cadmium sulfide powders as photocatalysts [97, 107, 143-145]. During this work we found also a new reaction type which was classified as semiconductor photocatalysis type B [45]. In contrast to type A reactions, where at least one oxidized and one reduced product is formed, type B reactions afford only one unique product, i.e., the semiconductor catalyzes a photoaddition reaction (see below). 

The synthesis of the / NA/AlP04-5 and that of the cadmium sulfide/zeolite Y composites are typical of the preparation methods used to generate zeotype-based host-guest materials. These usually involve multi-step syntheses. Typical reaction sequences are ... 

Tributylphosphine sulfide has been used as a co-catalyst with dicobalt octacarbonyl for the Pawson-Khand reaction. Thermolysis of a mixture of cadmium chloride and trioctylphosphine sulfide at 250 °C has been used as a route to the formation of nanocrystalline cadmium sulfide." A complex of triphenylphosphine sulfide with a silver-tungsten-iodine acceptor has been characterised by X-ray studies. Ferrocenylphosphine chalcogenides have attracted considerable interest as ligands. Complexes of the monophosphino-phosphine sulfide (269) with rhodium have been characterised." The disulfide (270) forms complexes with both gold(i) and gold(iii) acceptors," and a silver(i) complex of the diselenide (271) has been prepared. ... 

Preparation of Colloidal CdS. Colloidal CdS samples were prepared by precipitation from an aqueous surfactant solution. Aqueous sodium sulfide was slowly added to a stirred solution of cadmium chloride plus surfactant, which produced a clear, yellow-orange colloidal sample of cadmium sulfide. The particle sizes of the colloids were on the order of 250-300 A in radius. There was no observable change in the particle radius upon addition of MV to the CdS colloids. Furthermore, in the absence of surfactant CdS rapidly precipitates from solution. 

Photochemistry of Titanium Dioxide Colloids. Another semiconductor colloid used in our studies is titanium dioxide which has a band gap of 3.2 eV. As in the case of cadmium sulfide, excitation of aqueous suspensions of this particle leads to electron-hole pair separation which can be intercepted with suitable redox reagents. In the absence of externally added solutes, the photogenerated electron-hole pair recombines to give the starting material and the light energy is dissipated to the medium as heat. Two types of TiOj samples are used in this study. TiOj prepared at high temperature (80°C) which behaves very similarly to commercial samples, and TlOj prepared at low temperature (35°C) which has a particle size of 300 100 A radius and shows different properties. 

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