Pub Date : 2025-02-27DOI: 10.1016/j.susc.2025.122727
Simon Albrechts, Léon Luntadila Lufungula, Christian Van Alsenoy, Frank Blockhuys
The adsorption of six derivatives of methane with different functional groups on the anatase (101) facet of titania (TiO2) is studied using quantum chemical calculations at the DFT/PBC level of theory. The strength of the resulting interactions is evaluated using (1) the adsorption energy, (2) an analysis of the electron density using the Quantum Theory of Atoms In Molecules (QTAIM), and (3) Hirshfeld bond orders. It is shown that the latter provide a straightforward way to gain internally consistent information on the relative strengths of the various interactions, which is much more detailed than the adsorption energies on the one hand and far less dependent on the bond type than the results of a QTAIM analysis on the other. The results show that amines, thiols, silanols and carboxylic acids adsorb rather poorly, while phosphonic and sulfonic acids bind strongly to the titania surface, in agreement with experimental observations.
{"title":"Adsorption of organic molecules on titania: The advantages of using bond orders to gauge interaction strength","authors":"Simon Albrechts, Léon Luntadila Lufungula, Christian Van Alsenoy, Frank Blockhuys","doi":"10.1016/j.susc.2025.122727","DOIUrl":"10.1016/j.susc.2025.122727","url":null,"abstract":"<div><div>The adsorption of six derivatives of methane with different functional groups on the anatase (101) facet of titania (TiO<sub>2</sub>) is studied using quantum chemical calculations at the DFT/PBC level of theory. The strength of the resulting interactions is evaluated using (1) the adsorption energy, (2) an analysis of the electron density using the Quantum Theory of Atoms In Molecules (QTAIM), and (3) Hirshfeld bond orders. It is shown that the latter provide a straightforward way to gain internally consistent information on the relative strengths of the various interactions, which is much more detailed than the adsorption energies on the one hand and far less dependent on the bond type than the results of a QTAIM analysis on the other. The results show that amines, thiols, silanols and carboxylic acids adsorb rather poorly, while phosphonic and sulfonic acids bind strongly to the titania surface, in agreement with experimental observations.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"756 ","pages":"Article 122727"},"PeriodicalIF":2.1,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143534221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This work examines the structural stability of the novel Con nanocluster functionalized WS2 nanosheets for their subsequent application in trapping C4F7N decomposition gas molecules. Thermodynamic date confirmed the geometrical stability of the Con cluster functionalized WS2 nanosheets. The strong interaction between the Co clusters and surface S atoms of WS2 nanosheet was addressed using the electron density difference and density of states analyses. The suggested C4F7N decomposition gases including C2N2, C3F7, CF3CN and COF2 exhibited strong chemical reaction on the substrate, except for CF4 molecule, for which the weak physical adsorption occurred on the surface of Co functionalized WS2. The results exhibited that most of the C4F7N decomposition gases adsorption changed the electronic properties of Co functionalized WS2 notably, especially in the case of gases establishing strong covalent bonds to the Co atom. Consequently, Con nanocluster functionalized WS2 represented semiconductor and may be outstanding candidates for sensing C4F7N decomposition molecules.
{"title":"Engineering the surface of WS2 nanosheets by Con clusters to improve the adsorption of C4F7N decomposition gas molecules: A DFT study","authors":"Rafid Jihad Albadr , Waam mohammed taher , Roopashree R , Aditya Kashyap , Suman Saini , Piyus Kumar Pathak , RSK Sharma , Mariem Alwan , Mahmood Jasem Jawad , Aseel Smerat","doi":"10.1016/j.susc.2025.122722","DOIUrl":"10.1016/j.susc.2025.122722","url":null,"abstract":"<div><div>This work examines the structural stability of the novel Co<sub>n</sub> nanocluster functionalized WS<sub>2</sub> nanosheets for their subsequent application in trapping C<sub>4</sub>F<sub>7</sub>N decomposition gas molecules. Thermodynamic date confirmed the geometrical stability of the Co<sub>n</sub> cluster functionalized WS<sub>2</sub> nanosheets. The strong interaction between the Co clusters and surface S atoms of WS<sub>2</sub> nanosheet was addressed using the electron density difference and density of states analyses. The suggested C<sub>4</sub>F<sub>7</sub>N decomposition gases including C<sub>2</sub>N<sub>2</sub>, C<sub>3</sub>F<sub>7</sub>, CF<sub>3</sub>CN and COF<sub>2</sub> exhibited strong chemical reaction on the substrate, except for CF<sub>4</sub> molecule, for which the weak physical adsorption occurred on the surface of Co functionalized WS<sub>2</sub>. The results exhibited that most of the C<sub>4</sub>F<sub>7</sub>N decomposition gases adsorption changed the electronic properties of Co functionalized WS<sub>2</sub> notably, especially in the case of gases establishing strong covalent bonds to the Co atom. Consequently, Co<sub>n</sub> nanocluster functionalized WS<sub>2</sub> represented semiconductor and may be outstanding candidates for sensing C<sub>4</sub>F<sub>7</sub>N decomposition molecules.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"757 ","pages":"Article 122722"},"PeriodicalIF":2.1,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-23DOI: 10.1016/j.susc.2025.122726
Zilian Tian, Lu Yang, Jianlin He, Huaidong Liu, Xiaotong Yang, Hang Yang, Yao Dong, Wei Zhao
In this paper, density functional theory (DFT) is used to systematically study the S-vacancy defect system in a single layer of 2H-GaS and the effects of biaxial tensile and compressive strains on the geometric structure, electronic structure, and optical properties of this defect system are discussed. The study's results show that different defect atoms can influence the formation of defect systems, among which S-vacancy defects show high stability.Under biaxial tensile strain, the band gap of GaS shows a significant reduction under compressive strain,it tends to decrease and then increase. Optical property analysis shows that tensile strain causes a blue shift in the defective system's ultraviolet (UV) reflectivity and absorption coefficient, while compressive strain significantly increases these coefficients. The above results provide a theoretical basis for applying GaS-based materials in sensors, flexible electronics, and optoelectronic devices.
{"title":"The effect of biaxial strain on the optoelectronic properties of a single-layer 2H-GaS system with S vacancies","authors":"Zilian Tian, Lu Yang, Jianlin He, Huaidong Liu, Xiaotong Yang, Hang Yang, Yao Dong, Wei Zhao","doi":"10.1016/j.susc.2025.122726","DOIUrl":"10.1016/j.susc.2025.122726","url":null,"abstract":"<div><div>In this paper, density functional theory (DFT) is used to systematically study the S-vacancy defect system in a single layer of 2H-GaS and the effects of biaxial tensile and compressive strains on the geometric structure, electronic structure, and optical properties of this defect system are discussed. The study's results show that different defect atoms can influence the formation of defect systems, among which S-vacancy defects show high stability.Under biaxial tensile strain, the band gap of GaS shows a significant reduction under compressive strain,it tends to decrease and then increase. Optical property analysis shows that tensile strain causes a blue shift in the defective system's ultraviolet (UV) reflectivity and absorption coefficient, while compressive strain significantly increases these coefficients. The above results provide a theoretical basis for applying GaS-based materials in sensors, flexible electronics, and optoelectronic devices.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"756 ","pages":"Article 122726"},"PeriodicalIF":2.1,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143534222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-22DOI: 10.1016/j.susc.2025.122724
Marija Stojkovska , Jose Eduardo Barcelon , Daniele Perilli , Gianangelo Bracco , Giovanni Carraro , Marco Smerieri , Mario Rocca , Luca Vattuone , Luca Vaghi , Antonio Papagni , Cristiana Di Valentin , Letizia Savio
Pd-cyclometallated compounds may be relevant for catalytic purposes, but very little is known about their interactions with metal substrates.
Here we report a combined low-temperature scanning tunnelling microscopy and density functional theory investigation on the interaction of the cyclometallated compound C22H14Br2N2Pd2Cl2 on Ag(110). Upon deposition at low temperature the molecules adsorb in a disordered manner on the surface but, upon annealing to room temperature, a cross-coupling reaction between molecular fragments occurs and ordered ad-layers are observed.
Comparison of the present result with those previously reported for deposition at 300 K and annealing to higher temperature shows that the final product of the cross-coupling reaction is a different di-phenyl-bi-pyridine isomer. Therefore, we confirm the presence of a rich chemistry at the base of the cyclometallate-metal interaction, that significantly modifies the nature of the compounds, and we envisage the possibility to tune the final product of cross-coupling reactions by selecting the suitable preparation protocol.
{"title":"Selection of cross-coupling reaction products from Pd-cyclometalled complexes deposited on Ag(110) by tuning preparation conditions.","authors":"Marija Stojkovska , Jose Eduardo Barcelon , Daniele Perilli , Gianangelo Bracco , Giovanni Carraro , Marco Smerieri , Mario Rocca , Luca Vattuone , Luca Vaghi , Antonio Papagni , Cristiana Di Valentin , Letizia Savio","doi":"10.1016/j.susc.2025.122724","DOIUrl":"10.1016/j.susc.2025.122724","url":null,"abstract":"<div><div>Pd-cyclometallated compounds may be relevant for catalytic purposes, but very little is known about their interactions with metal substrates.</div><div>Here we report a combined low-temperature scanning tunnelling microscopy and density functional theory investigation on the interaction of the cyclometallated compound C<sub>22</sub>H<sub>14</sub>Br<sub>2</sub>N<sub>2</sub>Pd<sub>2</sub>Cl<sub>2</sub> on Ag(110). Upon deposition at low temperature the molecules adsorb in a disordered manner on the surface but, upon annealing to room temperature, a cross-coupling reaction between molecular fragments occurs and ordered ad-layers are observed.</div><div>Comparison of the present result with those previously reported for deposition at 300 K and annealing to higher temperature shows that the final product of the cross-coupling reaction is a different di-phenyl-bi-pyridine isomer. Therefore, we confirm the presence of a rich chemistry at the base of the cyclometallate-metal interaction, that significantly modifies the nature of the compounds, and we envisage the possibility to tune the final product of cross-coupling reactions by selecting the suitable preparation protocol.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"756 ","pages":"Article 122724"},"PeriodicalIF":2.1,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143510118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-21DOI: 10.1016/j.susc.2025.122723
Wenli Xie , Bin Cui , Desheng Liu
The availability of sensitive and effective materials for the detection and separation of mixed gases is essential for the development of molecular gas-sensitive elements. In this study, the structural stability of five colorless and odorless gase molecules (H2, O2, N2, NO, and CO) adsorbed on O+Pd13, an oxygen-loaded cluster, was investigated through determinations of their electronic structure and kinetic stability. The results demonstrate that the changes which occur in the large surface-to-body ratio and porous microstructure of the O+Pd13 cluster upon adsorption of the small gas molecules make it a suitable candidate for use as a nano-gas-sensitive material.
{"title":"Theoretical study of gas-sensitive properties of O+Pd13 clusters","authors":"Wenli Xie , Bin Cui , Desheng Liu","doi":"10.1016/j.susc.2025.122723","DOIUrl":"10.1016/j.susc.2025.122723","url":null,"abstract":"<div><div>The availability of sensitive and effective materials for the detection and separation of mixed gases is essential for the development of molecular gas-sensitive elements. In this study, the structural stability of five colorless and odorless gase molecules (H<sub>2</sub>, O<sub>2</sub>, N<sub>2</sub>, NO, and CO) adsorbed on O+Pd<sub>13</sub>, an oxygen-loaded cluster, was investigated through determinations of their electronic structure and kinetic stability. The results demonstrate that the changes which occur in the large surface-to-body ratio and porous microstructure of the O+Pd<sub>13</sub> cluster upon adsorption of the small gas molecules make it a suitable candidate for use as a nano-gas-sensitive material.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"756 ","pages":"Article 122723"},"PeriodicalIF":2.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-21DOI: 10.1016/j.susc.2025.122721
Kingsley C. Chukwu , Líney Árnadóttir
Acetic acid decomposition on Pt (111) in the presence of co-adsorbed water is a good model system for oxygenate decomposition on Pt (111) in aqueous phase, with application in hydrogen production and biomass conversion. Here we present a density functional theory (DFT) theory calculation of how co-adsorbed water affects different bond cleavages of acetic acid decomposition on Pt (111). The presence of co-adsorbed water generally enhances OH bond cleavage while inhibiting OCO and OCOH bond cleavage. The influence of co-adsorbed water on CH bond cleavage varies the most and depends on the nature of the transition state and how co-adsorbed water stabilizes the initial and final state. Although these trends are useful as general guidance, they are not sufficient to predict the effect on a complex reaction network such as acetic acid decomposition on Pt (111) which has several parallel reaction paths with similar energies.
In the absence of co-adsorbed water, the two lowest energy pathways are decarboxylation (DCX) and decarbonylation (DCN) pathways through a common CH2COO intermediate, in which the DCX pathway (CH bond cleavage of CH2COO) is more favorable than DCN pathway (OCO bond cleavage of CH2COO). In the presence of co-adsorbed water, the energy difference between CH bond cleavage and OCO bond cleavage of CH2COO increases, suggesting an increase in the favorability of acetic acid decarboxylation (formation of carbon dioxide) over acetic acid decarbonylation (formation of carbon monoxide) on Pt (111).
{"title":"Effects of co-adsorbed water on different bond cleavages involved in acetic acid decomposition on Pt (111)","authors":"Kingsley C. Chukwu , Líney Árnadóttir","doi":"10.1016/j.susc.2025.122721","DOIUrl":"10.1016/j.susc.2025.122721","url":null,"abstract":"<div><div>Acetic acid decomposition on Pt (111) in the presence of co-adsorbed water is a good model system for oxygenate decomposition on Pt (111) in aqueous phase, with application in hydrogen production and biomass conversion. Here we present a density functional theory (DFT) theory calculation of how co-adsorbed water affects different bond cleavages of acetic acid decomposition on Pt (111). The presence of co-adsorbed water generally enhances O<img>H bond cleavage while inhibiting OC<img>O and OC<img>OH bond cleavage. The influence of co-adsorbed water on C<img>H bond cleavage varies the most and depends on the nature of the transition state and how co-adsorbed water stabilizes the initial and final state. Although these trends are useful as general guidance, they are not sufficient to predict the effect on a complex reaction network such as acetic acid decomposition on Pt (111) which has several parallel reaction paths with similar energies.</div><div>In the absence of co-adsorbed water, the two lowest energy pathways are decarboxylation (DCX) and decarbonylation (DCN) pathways through a common CH<sub>2</sub>COO intermediate, in which the DCX pathway (C<img>H bond cleavage of CH<sub>2</sub>COO) is more favorable than DCN pathway (OC<img>O bond cleavage of CH<sub>2</sub>COO). In the presence of co-adsorbed water, the energy difference between C<img>H bond cleavage and OC<img>O bond cleavage of CH<sub>2</sub>COO increases, suggesting an increase in the favorability of acetic acid decarboxylation (formation of carbon dioxide) over acetic acid decarbonylation (formation of carbon monoxide) on Pt (111).</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"756 ","pages":"Article 122721"},"PeriodicalIF":2.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143510119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-20DOI: 10.1016/j.susc.2025.122714
Charles T. Campbell , Jan Fingerhut , Alec M. Wodtke
The energies of adsorbates containing H, C, O, N and I, that are of interest as intermediates and/or solvents in heterogeneous catalytic reactions have been measured accurately on clean and well-defined single crystal surfaces by a variety of methods, including temperature programmed desorption (TPD), pulsed molecular beam (PMB) surface residence time measurements, and singe crystal adsorption calorimetry (SCAC). In 2016, Silbaugh and Campbell1 published a large collection of those experimental adsorption energies which were consider to be particularly reliable based on reproducibility by other groups, comparisons to results for closely related systems, and/or reliability of other results reported by the same group. That database included the enthalpies and energies of 81 molecular and dissociative adsorption reactions that were measured on many different metal single crystal surfaces, as well as the standard enthalpies of formation of the adsorbates thus produced. In this paper, we tabulate the enthalpies and energies of an additional set of 26 molecular and dissociative adsorption reactions that were measured on 7 different metal single crystal faces of 5 different late transition metals (Pt, Pd, Ni, Cu and Au), based on more recent measurements from our own groups. We also tabulate the standard heats of formation of the 26 adsorbates thus produced. Taken together, these databases provide 107 benchmark energies for validating the energy accuracies of computational methods used for estimating surface reaction energies and building microkinetic models of catalytic reactions.
{"title":"Experimental energies of formation reactions for adsorbates on late transition metal surfaces: A database update","authors":"Charles T. Campbell , Jan Fingerhut , Alec M. Wodtke","doi":"10.1016/j.susc.2025.122714","DOIUrl":"10.1016/j.susc.2025.122714","url":null,"abstract":"<div><div>The energies of adsorbates containing H, C, O, N and I, that are of interest as intermediates and/or solvents in heterogeneous catalytic reactions have been measured accurately on clean and well-defined single crystal surfaces by a variety of methods, including temperature programmed desorption (TPD), pulsed molecular beam (PMB) surface residence time measurements, and singe crystal adsorption calorimetry (SCAC). In 2016, Silbaugh and Campbell<sup>1</sup> published a large collection of those experimental adsorption energies which were consider to be particularly reliable based on reproducibility by other groups, comparisons to results for closely related systems, and/or reliability of other results reported by the same group. That database included the enthalpies and energies of 81 molecular and dissociative adsorption reactions that were measured on many different metal single crystal surfaces, as well as the standard enthalpies of formation of the adsorbates thus produced. In this paper, we tabulate the enthalpies and energies of an additional set of 26 molecular and dissociative adsorption reactions that were measured on 7 different metal single crystal faces of 5 different late transition metals (Pt, Pd, Ni, Cu and Au), based on more recent measurements from our own groups. We also tabulate the standard heats of formation of the 26 adsorbates thus produced. Taken together, these databases provide 107 benchmark energies for validating the energy accuracies of computational methods used for estimating surface reaction energies and building microkinetic models of catalytic reactions.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"756 ","pages":"Article 122714"},"PeriodicalIF":2.1,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143474740","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-19DOI: 10.1016/j.susc.2025.122713
Michael E. Floto , J. Ehren Eichler , C. Buddie Mullins
We present experimental evidence for the activation of water and further reaction with ethane on a Mn/Au surface to form CO2(g) and H2(g). Additionally, we observe competitive chemisorption between water and carbon monoxide that resulted in water displacing carbon monoxide from a Mn/Au surface at 77 K. This model study unveils fundamental information about the role metallic manganese could be playing in highly energy relevant processes such as, water gas shift reaction and steam reforming of small alkanes.
{"title":"Water activation and reaction with ethane to form CO2(g) and H2(g) on a Mn/Au surface","authors":"Michael E. Floto , J. Ehren Eichler , C. Buddie Mullins","doi":"10.1016/j.susc.2025.122713","DOIUrl":"10.1016/j.susc.2025.122713","url":null,"abstract":"<div><div>We present experimental evidence for the activation of water and further reaction with ethane on a Mn/Au surface to form CO<sub>2</sub>(g) and H<sub>2</sub>(g). Additionally, we observe competitive chemisorption between water and carbon monoxide that resulted in water displacing carbon monoxide from a Mn/Au surface at 77 K. This model study unveils fundamental information about the role metallic manganese could be playing in highly energy relevant processes such as, water gas shift reaction and steam reforming of small alkanes.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"756 ","pages":"Article 122713"},"PeriodicalIF":2.1,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143471629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.susc.2025.122712
Dongliang Liu
First-principles calculations are performed to investigate the adsorption of nitrogen atom on the HfC and TaC (0 0 1) surface. The (√2 × √2) R45° supercell slabs are employed to calculate the adsorption at 0.5 monolayer coverage. In our calculations, the exchange-correlation potential is treated with the revised version of the Perdew-Burke-Ernzerhof (RPBE) functional. Our results show that the adsorption of N atom is a large exothermic process, indicating the interactions between N atom and the (0 0 1) surfaces are strong. The preferred adsorption site of N atom is MMC (M = Hf or Ta) site on the (0 0 1) surfaces. The results from Mulliken charges, bond population and density of states (DOS) demonstrate that N–C bonds in N/HfC (0 0 1) has more covalent characters than that in N/TaC(001). Meanwhile, N–Ta bond exhibits more covalent characters than N–Hf bond. Compared with the interactions of O atom and the (0 0 1) surfaces, the covalent interaction of N atom and the HfC (0 0 1) surface is weak, while the interaction between N atom and the TaC (0 0 1) surface is strong. Our results may provide basic information intended as a reference for the further development of HfC and TaC thermal protection materials.
{"title":"Adsorption of nitrogen atom on the (001) surface of HfC and TaC: A first-principles study","authors":"Dongliang Liu","doi":"10.1016/j.susc.2025.122712","DOIUrl":"10.1016/j.susc.2025.122712","url":null,"abstract":"<div><div>First-principles calculations are performed to investigate the adsorption of nitrogen atom on the HfC and TaC (0 0 1) surface. The (√2 × √2) R45° supercell slabs are employed to calculate the adsorption at 0.5 monolayer coverage. In our calculations, the exchange-correlation potential is treated with the revised version of the Perdew-Burke-Ernzerhof (RPBE) functional. Our results show that the adsorption of N atom is a large exothermic process, indicating the interactions between N atom and the (0 0 1) surfaces are strong. The preferred adsorption site of N atom is MMC (M = Hf or Ta) site on the (0 0 1) surfaces. The results from Mulliken charges, bond population and density of states (DOS) demonstrate that N–C bonds in N/HfC (0 0 1) has more covalent characters than that in N/TaC(001). Meanwhile, N–Ta bond exhibits more covalent characters than N–Hf bond. Compared with the interactions of O atom and the (0 0 1) surfaces, the covalent interaction of N atom and the HfC (0 0 1) surface is weak, while the interaction between N atom and the TaC (0 0 1) surface is strong. Our results may provide basic information intended as a reference for the further development of HfC and TaC thermal protection materials.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"755 ","pages":"Article 122712"},"PeriodicalIF":2.1,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143422074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
It is known that atomic layer deposition (ALD) of Al2O3 using trimethylaluminum (TMA) on transition metal surfaces is dependent to the type of the metal element, so that only coinage metal surfaces show delayed nucleation. In this study, the molecular and dissociative adsorption of TMA on 20 transition metal surfaces were investigated using density functional theory (DFT) calculations. The adsorption energy of molecular TMA depends on the group numbers of the elements, so that late transition metals are expected to show weaker adsorption of TMA molecule compared to those on early transition metals. Dissociative adsorption of TMA is expected to spontaneously proceed on most transition metal surfaces. However, TMA is expected to have reversible molecular adsorption on the surfaces of Cu, Zn, Ag, and Cd. Together with low propensity toward oxidation, the nucleation delay of Al2O3 ALD on Cu and Ag can be explained.
{"title":"Adsorption of trimethylaluminum on period 4 and 5 transition metal surfaces","authors":"Hyobin Eom, Sungmin Lee, Yohan Choi, Bonggeun Shong","doi":"10.1016/j.susc.2025.122711","DOIUrl":"10.1016/j.susc.2025.122711","url":null,"abstract":"<div><div>It is known that atomic layer deposition (ALD) of Al<sub>2</sub>O<sub>3</sub> using trimethylaluminum (TMA) on transition metal surfaces is dependent to the type of the metal element, so that only coinage metal surfaces show delayed nucleation. In this study, the molecular and dissociative adsorption of TMA on 20 transition metal surfaces were investigated using density functional theory (DFT) calculations. The adsorption energy of molecular TMA depends on the group numbers of the elements, so that late transition metals are expected to show weaker adsorption of TMA molecule compared to those on early transition metals. Dissociative adsorption of TMA is expected to spontaneously proceed on most transition metal surfaces. However, TMA is expected to have reversible molecular adsorption on the surfaces of Cu, Zn, Ag, and Cd. Together with low propensity toward oxidation, the nucleation delay of Al<sub>2</sub>O<sub>3</sub> ALD on Cu and Ag can be explained.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"755 ","pages":"Article 122711"},"PeriodicalIF":2.1,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号