Surface chemistry of carbon dioxide revisited

Abstract

This review discusses modern developments in CO 2 surface chemistry by focusing on the work published since the original review by H. J. Freund and M.W. Roberts two decades ago (Surface Science Reports 25 (1996) 225-273). It includes relevant fundamentals pertaining to the topics covered in that earlier review, such as conventional metal and metal oxide surfaces and CO 2 interactions thereon. While UHV spectroscopy has routinely been applied for CO 2 gas-solid interface analysis, the present work goes further by describing surface-CO 2 interactions under elevated CO 2 pressure on non-oxide surfaces, such as zeolites, sulfides, carbides and nitrides. Furthermore, it describes salient in situ techniques relevant to the resolution of the interfacial chemistry of CO 2 , notably infrared spectroscopy and state-of-the-art theoretical methods, currently used in the resolution of solid and soluble carbonate species in liquid-water vapor, liquid-solid and liquid-liquid interfaces. These techniques are directly relevant to fundamental, natural and technological settings, such as heterogeneous and environmental catalysis and CO 2 sequestration.

Direct Carbonation of Glycerol with CO2 Catalyzed by Metal Oxides

“…One can see the intenseb ands at 1526 and 1387 cm À1 ,i na ddition to bands of lower intensity in the region from 1050 to 700 cm À1 ,a ll of whichr efer to the formation of polydentate carbonate species. [36][37][38][39][40] The FTIR spectrum of ZnO pressurized with CO 2 is similar to the spectrum reported for ZnCO 3 nanoparticles, [41] suggesting that some phase of zinc carbonate may be formed upon pressurization with CO 2 at the reaction conditions. www.chemphyschem.org XPS analysis of the ZnO catalystb efore anda fter the reaction did not indicate anym ajor change in the oxidation state of the zinc atom.…”

An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO2 Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates

“…The C1s spectrum for the Au surface showed an asymmetric band, which could be deconvoluted into three peaks that we assigned to sp 3 carbon (C-C/C-H, 284.8 eV) 61 , carbon with C-O(H) bonds (~286.1 eV) 61 , and carbonate (-CO3, ~288.1 eV) 61 (Figure 1a). For the Cu surface, two distinct symmetric bands were observed in the C1s region ( Figure 1b), which could be assigned to sp 3 carbon (284.8 eV) 61 62 63 and carbonate (~288.1 eV) 61 62 . The spectrum of the Pt surface could be deconvoluted into four peaks that can be assigned to sp 3 carbon (284.8 eV) 61 , carbon with C-O(H) bonds (~285.8 eV) 61 64 65 , chemisorbed CO2 (CO2,ad, 287.2 eV) 61 , and carbonate (~288.5 eV) 61 .…”

“…We find sp 3 carbon (adventitious carbon), carbonate, and chemisorbed CO2 as major surface species on Au, Cu and Pt, respectively ( Figure 1). 61 62 63 , C-O(H) (Eb~285.5 eV) 61 64 65 , CO2,ad (Eb~286.8 eV) 61 , and CO3 (Eb~288.1 eV) 61 .…”

Quantum-mechanical process of carbonate complex formation and large-scale anisotropy in the adsorption energy of CO2 on anatase TiO2Mishra1, Choudhary2, Roy3 et al. 2018Phys. Rev. Materials11190View full textAdd to dashboardCite

“…As shown inFig. 4(a), corresponding to the σ interactions, the resulting six eigenstates in increasing energy order are 3σ g , 2σ u , 4σ g , 3σ u , 5σ g * and 4σ u *[60,61]. The π interactions of the 3 3 block give rise to three hybridized states, namely, the bonding (1π u ), antibonding (2π u * ) and an occupied (1π g ) state which is purely of O-p y/z character.Upon bending in the xz plane, the linear symmetry of the CO 2 molecule[62] is broken and the O atoms come closer to initiate interactions among their orbitals.…”