Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides As Lewis Acidic Heterogeneous Catalysts
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molecules Review Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides David Lennon and John M. Winfield * School of Chemistry, University of Glasgow, G12 8QQ Glasgow, UK; [email protected] * Correspondence: John.Winfi[email protected]; Tel.: +44-141-563-7281 Academic Editor: Erhard Kemnitz Received: 1 December 2016; Accepted: 17 January 2017; Published: 28 January 2017 Abstract: Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials. Keywords: metal fluoride; metal fluoride; oxohalide; catalysis; lewis acid; oxychlorination; chlorofluorocarbon; chlorohydrocarbon 1. Introduction Close-packed, solid metal fluorides have, for the most part, relatively small surface areas, although in some cases the surface metal cations have significant Lewis acidity due to their highly electronegative fluoride anion nearest-neighbors. For heterogeneous catalysis, partially fluorinated oxide surfaces have often been preferred, in view of their significantly increased surface areas without great loss in Lewis acidity. The development of nanostructured metal fluorides, which has been rapid over the past 10–15 years [1], has resulted in renewed interest in the possible catalytic applications of these high-surface-area metal fluorides and it is timely to consider how they compare as catalysts with materials prepared by more conventional routes. Catalytic studies are described explicitly in other contributions to this themed collection; here, in the first part of the review, we describe some surface properties of what might be termed ‘competitor catalysts’. The emphasis is on various forms of aluminum fluoride and γ-alumina, which have been fluorinated using various fluorinating agents. Although fluorinated chromia is also an obvious comparator, its catalytic activity is not dealt with here, since we have very recently compiled a detailed account of this topic [2]. 2. Aluminum Fluorides and Halogenated Aluminas Two of the important aluminum fluorides, which can be regarded as precursors to nanoscale metal fluorides, are β-aluminum trifluoride and aluminum chlorofluoride (ACF). The former contains Molecules 2017, 22, 201; doi:10.3390/molecules22020201 www.mdpi.com/journal/molecules Molecules 2017, 22, 201 2 of 10 III a six-coordinate Al but, unlike α-AlF3, which is close-packed, has the more open hexagonal tungsten bronze (HTB) structure [3]. This phase behaves as a solid Lewis acid and has significant catalytic Molecules 2017, 22, 201 2 of 10 behavior [4]; a model for the coordinatively unsaturated surface AlIII species has been deduced [5]. In contrast,coordinate ACF AlIII was but, unlike developed α-AlF3 from, which industrial is close-packed, research has the in fluorocarbonmore open hexagonal chemistry tungsten [6]. bronze Judged by its chemical(HTB) structure behavior, [3]. This its Lewisphase behaves acidity as is a comparable solid Lewis acid to thatand has of liquidsignificant antimony catalytic pentafluoride,behavior [4]; a benchmarka model infor thethe field.coordinatively Synthesized unsaturated by halogen surface exchange AlIII species between has been solid deduced aluminum [5]. In contrast, trichloride ACF and variouswas chlorofluorocarbons,developed from industrial hydrochlorofluorocarbons research in fluorocarbon chemistry or hexafluoropropene, [6]. Judged by its chemical the reactions behavior, do not its Lewis acidity is comparable to that of liquid antimony pentafluoride, a benchmark in the field. result in complete replacement of Cl by F; the stoichiometry of the solid product is AlClxF3−x, with Synthesized by halogen exchange between solid aluminum trichloride and various chlorofluorocarbons, x being in the range 0.05–0.3. Surface areas are in the range 100–150 m2·g−1. The structure of the hydrochlorofluorocarbons or hexafluoropropene, the reactions do not result in complete replacement amorphous solid has been deduced at the atomic level from a number of spectroscopic techniques [7]. of Cl by F; the stoichiometry of the solid product is AlClxF3−x, with x being in the range 0.05–0.3. Surface Chlorineareas isare distributed in the range throughout 100–150 m2·g the−1. The solid, structure rather of than the amorphous in a discrete solid AlCl has3 beenphase, deduced and is at possibly the III III bridgedatomic to threelevel from Al acenters. number There of spectroscopic appear to techniques be three different [7]. Chlorine types is of distributed six-coordinated throughout Al .the solid,The defect rather spinelthan in oxide a discreteγ-alumina AlCl3 phase, is an and ideal is basepossib materially bridged to investigateto three AlIII thecenters. effects There of fluorination appear uponto an be oxide three surface.different Thetypes surface of six-coordinated properties depend AlIII. on both the reagent employed and the conditions used, as illustratedThe defect spinel in Table oxide1. γ-alumina is an ideal base material to investigate the effects of fluorination upon an oxide surface. The surface properties depend on both the reagent employed and the conditions used, as illustrated in TableTable 1. 1. Some properties of fluorinated γ-alumina [8]. Table 1. Some propertiesBETArea of fluorinatedFluorine γ-alumina [8]. Fluorination Conditions a Other Properties (m2·g−1) Content (%) BET Area Fluorine Fluorination Conditions a Other Properties SF static conditions, nominally room 2 −1 4 (m80–90·g )b Contentca. (%) 22 c Some Brønsted sites also temperature, 2 h, procedure repeated ×2 SF4 static conditions, nominally room 80–90 b ca. 22 c Some Brønsted sites also temperature, 2 h, procedure repeated ×2 γ-alumina present; possibly an SF 20% in N , flow conditions, 523 K, 2 h 67 47.1 4 2 γ-aluminaamorphous present; phase possibly also SF4 20% in N2, flow conditions, 523 K, 2 h 67 47.1 CHF 20% in N , then 100%, flow an amorphousα- and β-AlF phasepresent; also 3 2 d 58.4 3 CHF3 20% in N2, then 100%, flow 34 α- and β-AlF3 present; conditions, 623 K, total time 5 h 34 d 58.4 possibly an amorphous phase conditions, 623 K, total time 5 h possibly an amorphous phase a In all cases samples were calcined before use; b Before fluorination 110 m2·g−1; c Calculated from a radiotracer a b 2 −1 c study; Ind Before all cases fluorination samples were 240 m calcined2·g−1. before use; Before fluorination 110 m ·g ; Calculated from a radiotracer study; d Before fluorination 240 m2·g−1. TheseThese fluorinated fluorinated aluminas aluminas are are not not supported supported reagen reagents,ts, since since the the fluorine fluorine is incorporated is incorporated within within the surface,the surface, and and in somein some cases, cases, possibly possibly inin thethe bulkbulk to some some extent. extent. They They contrast contrast therefore therefore withwith materials,materials, such such as supportedas supported boron boron trifluoride trifluoride [[9],9], which have have been been used used widely widely as solid as solid Lewis Lewis acids. acids. TwoTwo of the of possiblethe possible surface surface species species that that have have been been suggestedsuggested are are shown shown in in Figure Figure 1. 1. Figure 1. Possible surface species derived from BF3 and oxides. Redrawn from Reference [9]. Figure 1. Possible surface species derived from BF3 and oxides. Redrawn from Reference [9]. The uptake of F by γ-alumina is slow when CHF3 is used. The process is initiated at the surface ofThe oxide uptake particles, of F by subsequentlyγ-alumina being is slow incorporated when CHF 3intois used. sub-surface The process regions. is The initiated reaction at the between surface of oxidesulfur particles, tetrafluoride subsequently and γ-alumina being incorporated is essentially into a hydrolysis; sub-surface the regions. course Theof the reaction reaction between has been sulfur tetrafluoridefollowed using and γ the-alumina radiotracers is essentially fluorine-18 a hydrolysis;and sulfur-35. the The course hydrolysis of the involves reaction the has replacement been followed usingof thesurface radiotracers hydroxyls fluorine-18 by F and the and partial sulfur-35. replacemen Thet hydrolysisof bridging Al-O-Al involves moieties the replacement by Al-F, with of the surface hydroxylsconcomitant by F and formation the partial of OSF replacement2 and SO2. These of bridging are not Al-O-Alstrongly moietiesadsorbed. by The Al-F, Lewis with acid the sites concomitant have disordered F/O environments rather than being fully fluorinated. When the SF4 treatment is performed formation of OSF2 and SO2.