Article
Chemistry, Physical
Xiaoxia Chang, Haocheng Xiong, Yifei Xu, Yaran Zhao, Qi Lu, Bingjun Xu
Summary: The abrupt change in potential between the electrode and the electrolyte acts as the driving force in electrochemical reactions, with the interfacial electric field impacting the stability and reactivity of adsorbed intermediates in surface mediated electrocatalytic reactions. Reliable measurement of the interfacial electric field is crucial in understanding its influence on the rate and product distribution in electrochemical reactions. The vibrational Stark effect can be used to assess the interfacial electric field strength, but may be complicated by the dynamical dipole coupling effect of adsorbates, while the aggregate morphology, rather than the size and shape of individual catalyst particles, has a more prominent impact on the interfacial electric field.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
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, Multidisciplinary
Zixu Tao, Adam J. Pearce, James M. Mayer, Hailiang Wang
Summary: In this study, the mechanism of CO2 reduction to CO on Au catalyst was investigated using an improved spectroelectrochemical system. The Au surface was found to restructure, leading to an increased number of bridge sites for CO adsorption. It was shown that bridge-bonded *CO species (*COB) are active intermediates for CO2 reduction to CO on the Au electrode.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Justus S. Diercks, Juan Herranz, Maximilian Georgi, Natasa Diklic, Piyush Chauhan, Kathrin Ebner, Adam H. Clark, Maarten Nachtegaal, Alexander Eychmuller, Thomas J. Schmidt
Summary: Palladium is an electrocatalyst that can selectively generate carbon monoxide or formate at high and low overpotentials, respectively. Previous studies have been inconclusive about palladium's ability to form a hydride phase and its effect on CO2 reduction reaction (CO2RR) selectivity. This study used electrochemical measurements and in situ X-ray absorption spectroscopy to reveal the strong influence of adsorbed CO on the formation rate of Pd-hydride, and confirmed the complete formation of beta-phase PdHx at all applied potentials under CO2RR conditions.
Article
Chemistry, Physical
Jerry LaRue, Boyang Liu, Gabriel L. S. Rodrigues, Chang Liu, Jose Antonio Garrido Torres, Simon Schreck, Elias Diesen, Matthew Weston, Hirohito Ogasawara, Fivos Perakis, Martina Dell'Angela, Flavio Capotondi, Devon Ball, Conner Carnahan, Gary Zeri, Luca Giannessi, Emanuele Pedersoli, Denys Naumenko, Peter Amann, Ivaylo Nikolov, Lorenzo Raimondi, Carlo Spezzani, Martin Beye, Johannes Voss, Hsin-Yi Wang, Filippo Cavalca, Jorgen Gladh, Sergey Koroidov, Frank Abild-Pedersen, Manuel Kolb, Piter S. Miedema, Roberto Costantini, Tony F. Heinz, Alan C. Luntz, Lars G. M. Pettersson, Anders Nilsson
Summary: This study reports on the desorption and oxidation of carbon monoxide induced by 400 nm femtosecond laser excitation on the O/Ru(0001) surface. Time-resolved x-ray absorption spectroscopy was used to probe the reaction and detect transient CO species with different orientations. The results were compared to previous experiments at the O K-edge.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Justus S. Diercks, Juan Herranz, Maximilian Georgi, Natasa Diklic, Piyush Chauhan, Kathrin Ebner, Adam H. Clark, Maarten Nachtegaal, Alexander Eychmueller, Thomas J. Schmidt
Summary: Palladium is an increasingly investigated electrocatalyst for the electrochemical reduction of carbon dioxide. Its unique ability to yield carbon monoxide or formate at high vs low overpotentials has drawn attention. Previous studies have disagreed on the ability of palladium to form a hydride phase under CO2 reduction reaction conditions and its influence on selectivity. This study used an unsupported Pd-aerogel to investigate CO adsorption and PdHx formation. The results revealed the strong influence of surface-adsorbed CO on the formation rate of Pd-hydride.
Article
Chemistry, Multidisciplinary
Jingyun Ye, Donald G. Truhlar
Summary: This study compared seven choices of reference states for calculating equilibrium constants and transition state theory rate constants for flat surfaces, with some models being suitable for treating both mobile and localized adsorbates, while others are specific to localized or freely translating adsorbates. Models 6 and 7 were found to reduce computational costs by not requiring calculations of barrier heights for diffusion, and a simple ideal 2D hindered translator was noted for its physical high-temperature limit.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Inyong Hwang, Mingyun Kim, Jaeyeon Yu, Jihye Lee, Jun-Hyuk Choi, Su A. Park, Won Seok Chang, Jongwon Lee, Joo-Yun Jung
Summary: SEIRA spectroscopy utilizes near-field effects in nanostructures for highly sensitive detection, with a 10 nm thick MA achieving a record-high reflection difference SEIRA signal in experiments. MAs can be mass-produced through nanoimprint lithography and dry etching, offering a promising technological pathway for sensing and detection applications.
Article
Chemistry, Multidisciplinary
Xuan Peng, Ting Meng, Lilei Wang, Linxiu Cheng, Wenchao Zhai, Ke Deng, Chang-Qi Ma, Qingdao Zeng
Summary: This study investigated the assembly behaviors of a series of linear oligothiophene derivatives on the liquid-solid interface using scanning tunneling microscopy. The distribution of alkyl chains affected intermolecular interactions and led to different assembled structures. Moreover, oligothiophene derivatives with an even number of thiophene rings exhibited overall greater stability in their self-assembled structures compared to those with an odd number of rings. The orientation of alkyl chains greatly influenced intermolecular interactions and resulted in various self-assembly structures of the studied derivatives.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Analytical
Ryuta Kubo, Masashi Nakamura, Nagahiro Hoshi
Summary: Modification with a protonic ionic liquid containing [7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD)] [bis(pentafluoroethanesulfonyl)imide (beti)] improved the cathodic reactions of fuel cells on Pt(1 1 1) and Pt(1 1 0), but deactivated Pt(1 0 0). The study used infrared reflection absorption spectroscopy (IRRAS) to investigate PtOH inhibiting species and the adsorption geometries of [MTBD][beti] on different Pt surfaces. The results showed a decrease in PtOH bands and different adsorption patterns of MTBD and beti on the surfaces, explaining the enhanced activities and deactivation of the Pt surfaces.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Engineering, Chemical
Xia Wang, Fangli Duan
Summary: This study investigates the influence of benzene molecular coverage and relative orientation of substrate crystal surfaces on the adsorption structure of interfacial benzene molecules and substrate surface damage. The results show that during the approaching process, benzene molecules form different adsorption structures depending on the coverage and relative orientation. The bridging benzene molecules bonded with two substrates during the separation process cause more substrate damage in the monolayer coverage model than in the other models.
Article
Chemistry, Multidisciplinary
Masaya Miyamoto, Masahiko Hada
Summary: The NPO computational method was applied to analyze the IR intensities of CO molecules adsorbed on Pd nanoparticles, revealing different interaction mechanisms between CO and metal surfaces under different adsorption models.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Chemistry, Physical
Corey J. Kaminsky, Sophia Weng, Joshua Wright, Yogesh Surendranath
Summary: Electrodes chemically modified with molecular active sites are effective catalysts for energy conversion reactions. The study uncovers the different reaction mechanisms of a particular electrode in acetonitrile and aqueous media, revealing that catalysis is determined by the free energy of hydrogen binding, rather than the reduction potential of the parent molecule.
Article
Biochemistry & Molecular Biology
Thi Thuy Tien Vo, Quang Canh Vo, Vo Phuoc Tuan, Yinshen Wee, Hsin-Chung Cheng, I-Ta Lee
Summary: Carbon monoxide (CO) and CO-releasing molecules (CO-RMs) have shown therapeutic potential in cancer by delivering CO to target sites and exhibiting anti-cancer activities targeting proliferation, apoptosis, angiogenesis, and invasion. Reactive oxygen species (ROS) play dual roles in cancer physiology, which could be harnessed for therapeutic benefits. The main focus is to identify the signaling network by which CO-RMs exert their anticancer actions, with a potential impact on aerobic glycolysis and future development challenges in cancer therapy.
Article
Materials Science, Multidisciplinary
Shah Tanvir Ur Rahman Chowdhury, Hong Tang, John P. Perdew
Summary: In this study, we extended the dispersion interaction model to molecules adsorbed on curved surfaces, and applied it as an additive correction to density functionals for accurate calculations of binding energies and equilibrium distances. The results showed that the methods developed for cylindrical surfaces were consistent and provided reliable estimations for interactions with large systems.
Article
Chemistry, Physical
Erhao Gao, Wenjing Feng, Qi Jin, Li Han, Yi He
Summary: The influence of K-doping on the reactive oxygen species and elementary reactions of HCHO catalytic oxidation was investigated using density functional theory (DFT). The introduction of K-doping changed the electronic structures of Ce and O, facilitating the adsorption and activation of HCHO and O2 molecules, enhancing lattice oxygen mobility, and reducing the energy barrier for HCHO oxidation. K-doping also promoted the formation of hydroxyl groups, facilitating HCHO adsorption and oxidation.
Article
Chemistry, Physical
Hao Fu, Zhangliang Xu
Summary: In this study, the adsorption mechanisms and detection performance of formaldehyde, ammonia, and sulfur dioxide on undoped and metal-doped ZnO surfaces were investigated using density functional theory. The results showed that formaldehyde and ammonia were physically adsorbed on the undoped ZnO surface, while sulfur dioxide was weakly chemisorbed. The adsorption energy was enhanced when ZnO was doped with metals. These findings provide theoretical guidance for the application of ZnO substrate materials in gas sensitivity research.
Article
Chemistry, Physical
Atsushi Nomura, Tohru Kurosawa, Migaku Oda, Satoshi Demura, Shogo Kuwahara, Sora Kobayashi, Hideaki Sakata
Summary: The study investigates the tunneling spectra of 1T-TiSe2 in the CDW state and the dip structure below the Fermi level, aiming to determine whether this dip is a CDW gap. The answer to this question is crucial for understanding the driving mechanism of CDW.
Article
Chemistry, Physical
A. S. Petrov, D. I. Rogilo, A. I. Vergules, V. G. Mansurov, D. V. Sheglov, A. V. Latyshev
Summary: This study investigates Si mass transport and morphological transformations on the Si(111) surface during (root 3 x root 3)-Sn reconstruction formation and Si homoepitaxy. The research shows that the formation of different Sn phases at different temperatures affects the Si island nucleation and monatomic step shift, which in turn impact the morphology of the Sn/Si(111) interface. Electromigration-induced drift of disordered Sn domains leads to enhanced noncompensated Si mass transport and surface roughening.
Article
Chemistry, Physical
D. V. Gruznev, L. V. Bondarenko, A. Y. Tupchaya, A. A. Yakovlev, A. N. Mihalyuk, A. V. Zotov, A. A. Saranin
Summary: Deposition of thallium (Tl) onto the Au/Si(111)5 x 2 reconstruction followed by annealing results in the formation of a surface structure with 4 x 2 periodicity. The immiscibility of Au and Tl leads to the migration of Tl atoms over the Si chains. Thallium donates electrons to the surface, converting the metallic surface into an insulating state and altering the inter-chain distance within the array of Au atomic wires.
Article
Chemistry, Physical
Simone Giusepponi, Francesco Buonocore, Barbara Ferrucci, Massimo Celino
Summary: Using ab-initio calculations, the interaction between lead adatom and both clean and doped iron (100) surfaces was investigated. It was found that the lead adatom prefers to adsorb in the hollow site, which is more stable compared to the top and bridge sites, and in this position, it is energetically favorable over the iron adatom. Moreover, lead adsorbed in the hollow site of the iron (100) surface doped with chromium was found to create a more stable system compared to nickel-doped surfaces with an iron adatom in the same position. The study also explored inter-layer distances, bonding mechanisms, magnetic behaviors, and charge density differences. The results provide insights into the role of doping in the interaction between lead adatom and iron surface, and have implications for the analysis of corrosion processes caused by liquid lead.
Article
Chemistry, Physical
Shuo Zhang, Jin-Ho Choi
Summary: The recent synthesis of two-dimensional layered WSi2N4 has attracted attention due to its potential applications. This study investigates the catalytic performance of WSi2N4 monolayers with nitrogen vacancies in the hydrogen evolution reaction using first-principles calculations. The results show that the defective WSi2N4 monolayers exhibit remarkably high catalytic activity comparable to platinum catalysts. Electronic structure calculations also reveal the emergence of spin-polarized states due to the introduction of nitrogen vacancies.
Article
Chemistry, Physical
Xiaoyan Yu, Xin Cao, Wei Kang, Shanhua Chen, Ao Jiang, Yuhao Luo, Wenwei Deng
Summary: First-principles calculations were used to investigate the electronic properties of a TiO2 heterostructure modified with Bi2Te3 co-catalyst. The study revealed that the Bi2Te3/TiO2 interface introduced optimal band offsets, effectively suppressing electron-hole recombination and enhancing the utilization efficiency of photo-generated carriers. Additionally, the Bi2Te3 co-catalyst introduced extra catalytic active sites, further boosting the photo-catalytic hydrogen evolution efficiency.
Article
Chemistry, Physical
Filippo Longo, Emanuel Billeter, Selim Kazaz, Alessia Cesarini, Marin Nikolic, Aarati Chacko, Patrik Schmutz, Zbynek Novotny, Andreas Borgschulte
Summary: Alkaline water electrolysis is a simple and efficient method for renewable hydrogen production, utilizing cheap and abundant transition metals. The catalytic properties of Ni materials are enhanced by the formation of oxidized compounds on the surface. The high electrocatalytic activity of Ni (oxy)-hydroxides is directly related to water intercalation in the passivation layer, supporting the hypothesis of a water mediated OH- diffusion mechanism. The self-organization of the surface structure during passivation layer formation enables high electrode performance.
Article
Chemistry, Physical
Mohan Kumar Kuntumalla, Miriam Fischer, Alon Hoffman
Summary: By investigating the bonding, retention, and thermal stability of nitrogen in H-Diamond (100), it was found that nitrogen can partially recover its bonding with carbon atoms after high-temperature annealing, indicating a high thermal stability of nitrogen in diamond.
Article
Chemistry, Physical
Dong Yue, Liangying Wen, Rong Chen, Jianxin Wang, Zhongqing Yang
Summary: The adsorption behavior of Cl2 molecules on the TiC surface and the formation and transfer of reaction products were studied using first-principles ab initio calculations. The results show that the Cl atoms bonded to the surface Ti atoms are more stable, and the TiCl3 intermediate is easier to form than the TiCl2 intermediate.
Article
Chemistry, Physical
Yatao Wang, Peng Zhang, Hongjuan Li, Qiuju Xu, Shujun Liu, Xiaopeng Liu, Xuehua Guo, Yitao Li, Jinzhang Liu, Sen Dong, Zhi Wei Seh, Qianfan Zhang
Summary: In this study, the adsorption performance of two types of metal-organic frameworks (MOFs) for thiophene and benzene was experimentally investigated. The results showed that IZE-1 exhibited high selectivity and superior adsorption capacity for thiophene, especially at low concentrations. First-principles calculations and molecular dynamics simulations provided insights into the mechanism of thiophene adsorption and the high selectivity observed. This research demonstrates the potential of MOFs for thiophene adsorption, particularly at high concentrations.