Electric Double Layer at the Rutile (110) Surface. 4. Effect of Temperature and pH on the Adsorption and Dynamics of Ions
Adsorption of Rb+, Na+, Sr2+, and Cl– on hydroxylated (110) rutile surfaces was studied by molecular dynamics (MD) simulations. Our previous work was extended to the range of surface charge densities from −0.2 to +0.1 C/m2 (from −0.4 to +0.1 C/m2 for Sr2+) and to temperatures of 25, 150, and 250 °C....
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| Veröffentlicht in: | Journal of physical chemistry. C 2013-11, Vol.117 (44), p.22852-22866 |
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| creator | Předota, M Machesky, M. L Wesolowski, D. J Cummings, P. T |
| description | Adsorption of Rb+, Na+, Sr2+, and Cl– on hydroxylated (110) rutile surfaces was studied by molecular dynamics (MD) simulations. Our previous work was extended to the range of surface charge densities from −0.2 to +0.1 C/m2 (from −0.4 to +0.1 C/m2 for Sr2+) and to temperatures of 25, 150, and 250 °C. These conditions can be linked to experimental surface charge and pH values from macroscopic titrations of rutile powders with surfaces dominated by 110 crystal planes. Simulations revealed that Na+ and Sr2+ adsorb closer to the surface, shifting from predominately bidentate to tetradentate inner-sphere binding with increasing temperature, whereas Rb+ binding is predominately tetradentate at all temperatures. These differences are related to hydration energies, which must be partially overcome for inner-sphere binding and which decrease with increasing temperature and are lowest for Rb+. The interaction of Cl– with the rutile surface is generally less than that for cations because of repulsion by surface oxygen atoms. These MD results provide molecular-level context for the trends observed in our corresponding macroscopic surface charge titrations. Titration curves steepen in the order Rb+ < Na+ < Sr2+, reflecting the adsorption interactions related to ion charge, radius, and hydration energy. |
| doi_str_mv | 10.1021/jp407124p |
| format | Article |
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Effect of Temperature and pH on the Adsorption and Dynamics of Ions</title><source>ACS Publications</source><creator>Předota, M ; Machesky, M. L ; Wesolowski, D. J ; Cummings, P. T</creator><creatorcontrib>Předota, M ; Machesky, M. L ; Wesolowski, D. J ; Cummings, P. T ; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)</creatorcontrib><description>Adsorption of Rb+, Na+, Sr2+, and Cl– on hydroxylated (110) rutile surfaces was studied by molecular dynamics (MD) simulations. Our previous work was extended to the range of surface charge densities from −0.2 to +0.1 C/m2 (from −0.4 to +0.1 C/m2 for Sr2+) and to temperatures of 25, 150, and 250 °C. These conditions can be linked to experimental surface charge and pH values from macroscopic titrations of rutile powders with surfaces dominated by 110 crystal planes. Simulations revealed that Na+ and Sr2+ adsorb closer to the surface, shifting from predominately bidentate to tetradentate inner-sphere binding with increasing temperature, whereas Rb+ binding is predominately tetradentate at all temperatures. These differences are related to hydration energies, which must be partially overcome for inner-sphere binding and which decrease with increasing temperature and are lowest for Rb+. The interaction of Cl– with the rutile surface is generally less than that for cations because of repulsion by surface oxygen atoms. These MD results provide molecular-level context for the trends observed in our corresponding macroscopic surface charge titrations. Titration curves steepen in the order Rb+ < Na+ < Sr2+, reflecting the adsorption interactions related to ion charge, radius, and hydration energy.</description><identifier>ISSN: 1932-7447</identifier><identifier>EISSN: 1932-7455</identifier><identifier>DOI: 10.1021/jp407124p</identifier><language>eng</language><publisher>Columbus, OH: American Chemical Society</publisher><subject>Condensed matter: structure, mechanical and thermal properties ; Exact sciences and technology ; Physics ; Solid surfaces and solid-solid interfaces ; Structure and morphology; thickness ; Surfaces and interfaces; thin films and whiskers (structure and nonelectronic properties) ; Thin film structure and morphology</subject><ispartof>Journal of physical chemistry. 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L</creatorcontrib><creatorcontrib>Wesolowski, D. J</creatorcontrib><creatorcontrib>Cummings, P. T</creatorcontrib><creatorcontrib>Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)</creatorcontrib><title>Electric Double Layer at the Rutile (110) Surface. 4. Effect of Temperature and pH on the Adsorption and Dynamics of Ions</title><title>Journal of physical chemistry. C</title><addtitle>J. Phys. Chem. C</addtitle><description>Adsorption of Rb+, Na+, Sr2+, and Cl– on hydroxylated (110) rutile surfaces was studied by molecular dynamics (MD) simulations. Our previous work was extended to the range of surface charge densities from −0.2 to +0.1 C/m2 (from −0.4 to +0.1 C/m2 for Sr2+) and to temperatures of 25, 150, and 250 °C. These conditions can be linked to experimental surface charge and pH values from macroscopic titrations of rutile powders with surfaces dominated by 110 crystal planes. Simulations revealed that Na+ and Sr2+ adsorb closer to the surface, shifting from predominately bidentate to tetradentate inner-sphere binding with increasing temperature, whereas Rb+ binding is predominately tetradentate at all temperatures. These differences are related to hydration energies, which must be partially overcome for inner-sphere binding and which decrease with increasing temperature and are lowest for Rb+. The interaction of Cl– with the rutile surface is generally less than that for cations because of repulsion by surface oxygen atoms. These MD results provide molecular-level context for the trends observed in our corresponding macroscopic surface charge titrations. Titration curves steepen in the order Rb+ < Na+ < Sr2+, reflecting the adsorption interactions related to ion charge, radius, and hydration energy.</description><subject>Condensed matter: structure, mechanical and thermal properties</subject><subject>Exact sciences and technology</subject><subject>Physics</subject><subject>Solid surfaces and solid-solid interfaces</subject><subject>Structure and morphology; thickness</subject><subject>Surfaces and interfaces; thin films and whiskers (structure and nonelectronic properties)</subject><subject>Thin film structure and morphology</subject><issn>1932-7447</issn><issn>1932-7455</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><recordid>eNptkF9LwzAUxYsoOKcPfoMgCO6hMzdp0vVxuOkGA0Hnc7lLE9bRNSVJH_btzZzMF5_uv985cG6S3AMdA2XwvOsymgPLuotkAAVnaZ4JcXnus_w6ufF-R6ngFPggOcwbrYKrFZnZftNossKDdgQDCVtNPvpQx90TAB2Rz94ZVHpMsjGZGxNlxBqy1vtOOwy90wTbinQLYtsf8bTy1nWhjuPxMDu0uK-VP4qWtvW3yZXBxuu73zpMvl7n65dFunp_W75MVylykCGVQkJVwERzroWKEcUmQ1PgRBUSzUYxYZhARhXQYiKl0WAmuoqhjQSjcsaHycPJ1_pQl17VQautsm0bA5QATArOIzQ6QcpZ7502ZefqPbpDCbQ8PrY8Pzayjye2Q6-wMQ5bVfuzgOVFLqiEPw6VL3e2d22M-Y_fN3hjgeE</recordid><startdate>20131107</startdate><enddate>20131107</enddate><creator>Předota, M</creator><creator>Machesky, M. 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(ORNL), Oak Ridge, TN (United States)</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Journal of physical chemistry. C</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Předota, M</au><au>Machesky, M. L</au><au>Wesolowski, D. J</au><au>Cummings, P. T</au><aucorp>Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electric Double Layer at the Rutile (110) Surface. 4. Effect of Temperature and pH on the Adsorption and Dynamics of Ions</atitle><jtitle>Journal of physical chemistry. C</jtitle><addtitle>J. Phys. Chem. C</addtitle><date>2013-11-07</date><risdate>2013</risdate><volume>117</volume><issue>44</issue><spage>22852</spage><epage>22866</epage><pages>22852-22866</pages><issn>1932-7447</issn><eissn>1932-7455</eissn><abstract>Adsorption of Rb+, Na+, Sr2+, and Cl– on hydroxylated (110) rutile surfaces was studied by molecular dynamics (MD) simulations. Our previous work was extended to the range of surface charge densities from −0.2 to +0.1 C/m2 (from −0.4 to +0.1 C/m2 for Sr2+) and to temperatures of 25, 150, and 250 °C. These conditions can be linked to experimental surface charge and pH values from macroscopic titrations of rutile powders with surfaces dominated by 110 crystal planes. Simulations revealed that Na+ and Sr2+ adsorb closer to the surface, shifting from predominately bidentate to tetradentate inner-sphere binding with increasing temperature, whereas Rb+ binding is predominately tetradentate at all temperatures. These differences are related to hydration energies, which must be partially overcome for inner-sphere binding and which decrease with increasing temperature and are lowest for Rb+. The interaction of Cl– with the rutile surface is generally less than that for cations because of repulsion by surface oxygen atoms. These MD results provide molecular-level context for the trends observed in our corresponding macroscopic surface charge titrations. Titration curves steepen in the order Rb+ < Na+ < Sr2+, reflecting the adsorption interactions related to ion charge, radius, and hydration energy.</abstract><cop>Columbus, OH</cop><pub>American Chemical Society</pub><doi>10.1021/jp407124p</doi><tpages>15</tpages></addata></record> |
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| subjects | Condensed matter: structure, mechanical and thermal properties Exact sciences and technology Physics Solid surfaces and solid-solid interfaces Structure and morphology thickness Surfaces and interfaces thin films and whiskers (structure and nonelectronic properties) Thin film structure and morphology |
| title | Electric Double Layer at the Rutile (110) Surface. 4. Effect of Temperature and pH on the Adsorption and Dynamics of Ions |
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