The hydration structure of dissolved carbon dioxide from X-ray absorption spectroscopy

Lam, Royce K.; England, Alice H.; Smith, Jacob W.; Rizzuto, Anthony M.; Shih, Orion; Saykally, Richard J.

doi:10.1016/j.cplett.2015.05.039

Cited by 20 publications

(23 citation statements)

References 47 publications

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“…This mixing system was previously employed in XAS measurements of aqueous H 2 CO 3 and dissolved CO 2 . 42,43 Briefly, a dual syringe pump system (Teledyne-ISCO 260D) drives two solutions through a Microvolume Y-connector. The mixed solution then travels through a 50 µm inner diameter fused silica capillary to generate the liquid microjet.…”

Section: Introductionmentioning

confidence: 99%

Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy

Lam

Smith

Rizzuto

et al. 2017

The Journal of Chemical Physics

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The fractionation of ions at liquid interfaces and its effects on the interfacial structure are of vital importance in many scientific fields. Of particular interest is the aqueous carbonate system, which governs both the terrestrial carbon cycle and physiological respiration systems. We have investigated the relative fractionation of carbonate, bicarbonate, and carbonic acid at the liquid/vapor interface finding that both carbonate (CO 2 3) and carbonic acid (H 2 CO 3) are present in higher concentrations than bicarbonate (HCO 3) in the interfacial region. While the interfacial enhancement of a neutral acid relative to a charged ion is expected, the enhancement of doubly charged, strongly hydrated carbonate anion over the singly charged, less strongly hydrated bicarbonate ion is surprising. As vibrational sum frequency generation experiments have concluded that both carbonate and bicarbonate anions are largely excluded from the air/water interface, the present results suggest that there exists a significant accumulation of carbonate below the depletion region outside of the area probed by sum frequency generation.

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Section: Introductionmentioning

confidence: 99%

Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy

Lam

Smith

Rizzuto

et al. 2017

The Journal of Chemical Physics

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“…It is therefore ideal for probing liquid structure. Since introducing the use of liquid microjet technology in XAS of liquids in 2001, 45 we have employed this methodology to study a wide variety of phenomena in liquid systems, including ion solvation and pairing in water, 46,47 the solvation of lithium in propylene carbonate, 48 the hydrolysis of carbon dioxide, 49 and the structure of hydrated carbonic acid.…”

Section: -17mentioning

confidence: 99%

Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

Lam

Smith

Saykally

2016

The Journal of Chemical Physics

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While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atomspecific probe providing details of both inter-and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility. Published by AIP Publishing. [http://dx

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“…Reproduced with permission from[329]. Copyright (2014) PCCP Owner Societies.The hydration assimilation of CO 2 into the matrix of aqueous solutions has also been studied.Recent notable developments in this area show that aqueous CO 2 can be regarded as hydrophobic: namely, with a small hydrogen bond number (0.56 bond/CO 2 )[330,331] as shown inFigure 70.…”

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confidence: 99%

“…This overall reaction thus accounts for energetic contributions from (de)hydration and (de)solvation reactions of CO 2 (aq). Theoretical studies[330,331,335] suggest that the hydroxyl, and not the carbonyl, group of carbonic acid is strongly hydrated in aqueous solutions. Building upon multiple efforts attempting to isolate carbonic acid[336][337][338][339][340][341], the study of Adamczyk et al[340] measured the proton transfer rate to the bicarbonate anion upon electronic excitation of photoacid.…”

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Surface chemistry of carbon dioxide revisited

Taifan

Boily

Baltrušaitis

2016

Surface Science Reports

153

129

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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.

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The hydration structure of dissolved carbon dioxide from X-ray absorption spectroscopy

Cited by 20 publications

References 47 publications

Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy

Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy

Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

Surface chemistry of carbon dioxide revisited

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