Article
Chemistry, Physical
Katrin Blondal, Khachik Sargsyan, David H. Bross, Branko Ruscic, C. Franklin Goldsmith
Summary: This study extends a method for computing anharmonic thermophysical properties of adsorbates on metal surfaces to include libration or frustrated rotation. It uses classical phase space integration with Monte Carlo sampling to calculate the partition function of CO on Pt(111) and CH3OH on Cu(111), with a neural network potential energy surrogate. The results are benchmarked against direct state counting, and it is found that the phase space integration approach agrees excellently with the direct state counting results. Anharmonicity significantly contributes to the thermodynamic properties of CH3OH on Cu(111), while the difference between harmonic oscillator and phase space integration for CO on Pt(111) can be attributed to multiple binding sites. The study highlights the importance of a thorough description of the potential energy surface for weakly bound adsorbates like CH3OH. The obtained thermophysical properties are used to calculate free energies of adsorption, equilibrium constants, and Langmuir isotherms, showing that the choice of model greatly affects the resulting surface coverages in kinetic models.
Article
Chemistry, Multidisciplinary
Dmitriy Borodin, Oihana Galparsoro, Igor Rahinov, Jan Fingerhut, Michael Schwarzer, Stefan Horandl, Daniel J. Auerbach, Alexander Kandratsenka, Dirk Schwarzer, Theofanis N. Kitsopoulos, Alec M. Wodtke
Summary: This study presents a detailed kinetics analysis of NH3 thermal desorption rates from p(2 x 2) O/Pt(111). It is found that the adsorption of O-atoms on Pt(111) greatly reduces the desorption rate of NH3. A physical model is proposed to explain the interactions between adsorbed NH3 and O-atoms, and the model is fitted to derive the desorption rate constants. The results indicate a higher stabilization and rotational barrier for NH3 on p(2 x 2) O/Pt(111) compared to Pt(111). The study also highlights the importance of dispersion interactions for accurately predicting the NH3-O adsorbate-adsorbate interactions and NH3 binding energies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
David L. Molina, Maki Inagaki, Emiko Kazuma, Yousoo Kim, Michael Trenary
Summary: Reflection absorption infrared spectroscopy and temperature-programmed desorption experiments were carried out to investigate the properties of Pt/Cu(111) surfaces. Pt coverage on Cu(111) was varied from multilayer to 0.23 monolayer. As the Pt coverage decreased, isolated Pt atoms and Pt islands were observed, indicating the presence of Pt atoms embedded in the Cu(111) surface. Low coverages of Pt at different temperatures formed single atom alloys (SAAs) with surface Pt only present as isolated atoms replacing Cu atoms in the topmost atomic layer. Adsorption of CO on the Pt atoms of the SAAs led to red-shifted C-O stretch peaks compared to CO on Pt(111), indicating how nearby Cu atoms alter the Pt-CO bonding.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Mei Xue, Jianfeng Jia, Haishun Wu
Summary: The research investigates the impact of different structural units on the CO adsorption performance using density functional theory, and finds that Pt trimer catalyst exhibits a stronger CO adsorption capacity. The study also explores the effects of different Pt structural units on the C-O bond in CO molecules.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Junjie Chen, Linke Li
Summary: Density functional theory calculations were used to study the reaction mechanisms of methane autothermal reforming on Pt(1 1 1) surfaces. The results showed that formyl was the preferred adsorbed oxygen-containing species on the surface, and methane could be dissociated to form carbon via a series of steps including methane oxidation and dehydrogenation. Hydroxyl radicals were found to play a minor role in the overall reforming process, with their main relevance being the formation of methanol fragments from carbon adsorbed on the surface.
APPLIED SURFACE SCIENCE
(2021)
Article
Chemistry, Physical
Peng Chai, Zongfang Wu, Longxia Wu, Haocheng Wang, Cong Fu, Weixin Huang
Summary: In this study, the moisture effect on low-temperature CO oxidation on Pt(111) under near ambient pressure conditions was investigated using operando techniques. The results showed that moisture enhanced the CO oxidation rate on Pt(111) and the enhancement effect varied with reaction temperature. Characterization results provided evidence for the formation of reversibly adsorbed OH species and irreversibly adsorbed COOH species as the key surface intermediates resulting from water activation on Pt(111) at temperatures around 300 K. These findings contribute to the understanding of water-enhanced low-temperature CO oxidation on Pt(111) under near ambient pressure conditions.
Article
Chemistry, Physical
Peng Chai, Zongfang Wu, Longxia Wu, Haocheng Wang, Cong Fu, Weixin Huang
Summary: Fundamental studies of catalytic reaction mechanisms of working catalysts are important. In this study, an operando method was used to investigate the moisture effect on low-temperature CO oxidation on Pt(111). Experimental evidence shows that moisture can enhance the CO oxidation rate on Pt(111), and the enhancement effect varies with reaction temperature.
Article
Chemistry, Physical
Lin Zhang, Ling Yan, Jinlin Lu, Yi Zhang, Yansheng Yin
Summary: In this study, the adsorption behaviors of CO and CH3OH on Pt monolayer on different surfaces were investigated using density functional theory. It was found that Pt/WC has higher tolerance for CO poisoning compared to Pt/C, providing a theoretical basis for designing efficient catalysts.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Aleksandra Selivanova, Victoria G. Demina, Egor E. Aydakov, Andrey A. Saraev, Vasily V. Kaichev, Valerii Bukhtiyarov
Summary: The oxidation of methanol on a Pt(1 1 1) single crystal surface was found to start at around 350 K, producing mainly CO2 and methyl formate. Key intermediates in the reaction include CO and formaldehyde, with formates exhibiting low thermal stability and carbonates showing extremely high thermal stability. Carbonates, along with CO, can inhibit the oxidation of methanol on the platinum surface.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Analytical
Jonathan A. Mwanda, Angel Cuesta
Summary: This study investigated the electrochemical reduction of Ag+ on a cyanide-modified electrode, revealing the formation of an AgPt surface alloy on the platinum substrate without loss of the cyanide adlayer. The large negative shift of the Ag+/Ag redox couple was attributed to the strong affinity of Ag+ for the CN adlayer. Additionally, electrodeposited Ag could be reoxidized to yield Ag+ coordinated to the CN adlayer, leading to surface roughening and gradual transformation of the cyanide-modified Pt(111) to a cyanide-modified AgPt surface alloy on Pt(111) with successive cycling below 0.90 V.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Lin Hu, Zhe Zhang, Bao-Bing Zheng, Jin-Zhu Zhao
Summary: In this work, the different behaviors of a chemical reaction on the two surfaces of the two-dimensional ferroelectric In2Se3 catalyst were studied. The reduction reactions of organic formaldehyde and methanol on the surface of In2Se3 with a single In vacancy were investigated using first-principles. It was found that conductive electron states were localized in the vacancy region originating from the unpaired electrons of the dangling bonds. Considering the acidic environment of the reaction, hydrogen atoms were used to saturate the three dangling bonds in each In vacancy. The evolution of the total free energy of the reaction showed that the reduction reactions were more favorable on one surface compared to the other. The asymmetry of the two surfaces, which can be equivalently switched by external electric fields, suggests an effective approach for controlling catalytic reactions in practical applications.
SURFACES AND INTERFACES
(2023)
Article
Chemistry, Physical
Kenta Hayashi, Takeru Tomimori, Riku Sato, Naoto Todoroki, Toshimasa Wadayama
Summary: Simultaneous achievement of high hydrogen oxidation reaction (HOR) activity and suppressed hydrogen peroxide (H2O2) generation is desired for anode catalysts of polymer electrolyte fuel cells. 0.3 monolayer-thick-Pt-deposited Ir(111) exhibited three-fold higher HOR activity compared to Pt(111) and effectively suppressed H2O2 generation below the detection limit, offering valuable insights for catalyst development.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Joseph A. Smerdon, Vincent Fournee, Julian Ledieu, Katariina Pussi
Summary: In this study, carbon-60 molecules were deposited on the fcc Ni(111) surface and the surface of bulk hcp Co(0001) for the first time, and were measured using low-energy electron diffraction and scanning tunneling microscopy. The formation of an adlayer with predominantly (4 x 4) domains was observed in both cases, with other domains representing chiral epitaxial degeneracy. Annealing resulted in the formation of films with bright and dim molecules, with differences depending on the substrate. For C60 adsorption atop Ni(111), annealing led to the formation of vacancies beneath dim molecules and adatom nucleation below bright molecules.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Selwyn Hanselman, Federico Calle-Vallejo, Marc T. M. Koper
Summary: Surface platinum hydride structures on Pt(111) play a potentially important role in electrocatalysis and cathodic corrosion. Using thermodynamic methods and density functional theory, multiple surface hydride structures on Pt(111) were compared. These structures contain multiple monolayers of hydrogen that can bind subsurface or reconstruct the surface. Stable configurations share one monolayer of subsurface H stacking between the top two Pt layers. Our work provides insight into the operando surface state during low-potential reduction reactions on Pt(111) and shows a plausible precursor for cathodic corrosion.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Biochemistry & Molecular Biology
Merve Demirtas, Hande Ustunel, Daniele Toffoli
Summary: The catalytic activity of gold can be enhanced by introducing other metals to its surface. In this study, the effect of Pt doping on the catalytic activity of a Au(111) surface for methanol dehydrogenation was investigated using first-principles density functional theory. It was found that Pt surface doping significantly decreases the activation energy barrier of this reaction.
Article
Electrochemistry
Yuan Cheng, Tae-Sik Oh, Rachel Wilson, Raymond J. Gorte, John M. Vohs
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2017)
Article
Electrochemistry
M. Rahmanipour, Y. Cheng, T. M. Onn, A. Donazzi, J. M. Vohs, R. J. Gorte
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2017)
Article
Chemistry, Applied
Paul A. Pepin, Benjamin T. Diroll, Christopher B. Murray, John M. Vohs
TOPICS IN CATALYSIS
(2018)
Article
Chemistry, Applied
Daming Shi, John M. Vohs
Article
Chemistry, Physical
Cong Wang, Alexander V. Mironenko, Abhishek Raizada, Tianqi Chen, Xinyu Mao, Ashwin Padmanabhan, Dionisios G. Vlachos, Raymond J. Gorte, John M. Vohs
Article
Chemistry, Physical
Paul A. Pepin, Jennifer D. Lee, Christopher B. Murray, John M. Vohs
Article
Chemistry, Physical
Paul A. Pepin, Jennifer D. Lee, Alexandre C. Foucher, Christopher B. Murray, Eric A. Stach, John M. Vohs
JOURNAL OF PHYSICAL CHEMISTRY C
(2019)
Article
Chemistry, Physical
Yuan Cheng, Abhinav S. Raman, Julian Paige, Liang Zhang, Danyi Sun, Mavis U. Chen, Aleksandra Vojvodic, Raymond J. Gorte, John M. Vohs
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2019)
Article
Chemistry, Physical
Julian M. Paige, Yuan Cheng, Paul A. Pepin, Christopher D. Curran, Danyi Sun, Mavis U. Chen, Steven Mclntosh, John M. Vohs, Raymond J. Gorte
SOLID STATE IONICS
(2019)
Article
Chemistry, Physical
Tianqi Chen, John M. Vohs
Article
Chemistry, Physical
Tianyu Cao, Renjing Huang, Raymond J. Gorte, John M. Vohs
APPLIED CATALYSIS A-GENERAL
(2020)
Article
Chemistry, Physical
Arim Seong, Jeongwon Kim, Ohhun Kwon, Hu Young Jeong, Raymond J. Gorte, John M. Vohs, Guntae Kim
Article
Chemistry, Physical
Jian Chang, Zhuoming Feng, John M. Vohs, Raymond J. Gorte
Summary: The water-gas-shift (WGS) reaction was studied on Cu catalysts supported on modified MgAl2O4 (MAO) support using Atomic Layer Deposition (ALD) method. The study found that Cu/MAO catalysts prepared by ALD exhibited higher activity, while Cu catalysts with ZnO, CeO2, and Mn2O3 films showed minimal differences in activity compared to Cu/MAO catalyst. Cu catalysts prepared on CoO films showed slightly lower activity.
Article
Chemistry, Inorganic & Nuclear
Ching-Yu Wang, Kai Shen, Raymond J. Gorte, John M. Vohs
Summary: A simple method for incorporating various catalytic metals into the pores of SBA-15 using vapor-phase infiltration is presented. The study utilized Atomic Layer Deposition (ALD) to expose metal precursors on SBA-15, forming monolayer films inside the mesopores. The size and loading of the metal particles were determined using characterization techniques. The effect of surface composition on catalytic performance was also investigated.
Proceedings Paper
Electrochemistry
Y. Cheng, T. Oh, M. Rahmanipour, R. Wilson, R. J. Gorte, J. M. Vohs
SOLID OXIDE FUEL CELLS 15 (SOFC-XV)
(2017)