Article
Chemistry, Physical
Elisabeth M. Dietze, Lin Chen, Henrik Groenbeck
Summary: This study investigates the water formation reaction on Pd surfaces using first-principles density functional theory calculations and kinetic Monte Carlo simulations. The results show that the reaction rate is influenced by surface steps and point defects, and the main reaction path is temperature-dependent.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Maximilian Kastenmeier, Lukas Fusek, Fatema Mohamed, Christian Schuschke, Michal Ronovsky, Matteo Farnesi Camellone, Nataliya Tsud, Viktor Johanek, Stefano Fabris, Simone Piccinin, Josef Myslivec, Olaf Brummel, Yaroslava Lykhach, Tomas Skala, Joerg Libuda
Summary: The formation of the metal-oxide interface in the Pd/Co3O4(111) model catalyst was investigated using DFT, SRPES, and STM. The interaction between the metal and support led to charge transfer and the formation of atomically dispersed Pd2+ species and partially oxidized Pd delta + aggregates. The most energetically favorable configuration was atomically dispersed Pd2+ species on the Co3O4(111) surface. The partially oxidized Pd delta + and Pd4Ox aggregates served as nuclei for the growth of metallic Pd0 nanoparticles.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Eva Marie Freiberger, Fabian Duell, Christoph Wichmann, Udo Bauer, Hans-Peter Steinrueck, Christian Papp
Summary: The adsorption and thermal evolution of ethylene on Rh(1 1 1) surface were studied using advanced surface science techniques. The research revealed that ethylene initially adsorbs molecularly at 140 K in a symmetrical geometry, and upon heating, ethylidyne and methylidyne are formed, along with decomposition to carbides.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Chemistry, Physical
Haoyang Sun, Pengyuan Qiu, Yunxin Yang, Junxiao Liu, Libin Zhang, Zhen Liu
Summary: This study investigates the surface structure of bimetallic Pd/Au catalyst and the role of potassium acetate in the synthesis of vinyl acetate (VAc). By constructing different configurations of the Pd/Au (1 1 1) surface and using density functional theory, the research reveals that the presence of potassium ion enhances VAc formation. The configuration of Pd/Au (1 1 1) with two adjacent palladium atoms embedded on the gold surface shows the most favorable outcome for VAc synthesis.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Physical
Dingwang Yuan, Li Cai, Tuanping Xie, Heting Liao, Wangyu Hu
Summary: The study indicates that ordered Cu-Pd alloy surfaces containing isolated Pd atoms are highly efficient for the selective hydrogenation of acetylene, while adjacent Pd atom ensembles show strong catalytic activity towards other reactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Marvin C. Schmidt, Carsten Schroeder, Philipp A. Haugg, Ann-Katrin Baumann, Jan Smyczek, Swetlana Schauermann
Summary: We conducted a mechanistic study on the interaction between allyl cyanide (AC) and Pd(111), and observed the formation of different types of self-organized 2D layers at different temperatures. By using scanning tunneling microscopy and infrared reflection absorption spectroscopy, we obtained complementary information on the distribution and chemical structure of AC molecules in the self-organized 2D layers.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Yugai Huang, Hui-Li Lu, Zhao-Xu Chen
Summary: Density functional calculations and microkinetic simulations were performed to investigate the transformation of acetylene on Pd(111), M(111) and PdM(111) (M = Cu, Ag, Au) surfaces. The results showed linear correlation between adsorption energies on alloy surfaces and pure metal surfaces, and revealed a good linear relationship between co-adsorption energies of initial states and transition states. Microkinetic simulations indicated that the introduction of coinage metals can reduce the activity but promote the selectivity by lowering the barriers of certain elementary steps in the reaction network.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Buddhika S. A. Gedara, Michael Trenary
Summary: Scanning tunneling microscopy was used to compare the evolution of Pd islands on Ag(111) and Au(111) surfaces. Different behaviors were observed, with large Pd islands and vacancy pits forming on Ag(111), while smaller Pd islands and no vacancy pits were observed on Au(111). The annealing process resulted in Pd diffusion into the subsurface for both surfaces, but the behavior on Au(111) was significantly different due to the herringbone reconstruction providing higher binding energy sites.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Materials Science, Coatings & Films
Nassar Doudin, Kayahan Saritas, Sohrab Ismail-Beigi, Eric Altman
Summary: A highly ordered single layer of Fe silicate was successfully grown on Pd(111), with experimental and theoretical analyses providing insights into its structure and chemical properties. Subsequent investigation on hydrogenation of the layer showed potential for releasing the 2D material from the growth substrate.
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A
(2021)
Article
Materials Science, Multidisciplinary
Yuta Kataoka, Jun Haruyama, Osamu Sugino
Summary: We calculated the diffusion coefficient of hydrogen on metal surfaces using a method that combines diagonalization of the potential energy surface with transition state theory. By including quantum effects and entropy effects in the transition state theory without stochastic simulations, our method provides more accurate results. However, more sophisticated quantum mechanical schemes are needed for cryogenic temperatures.
Article
Chemistry, Physical
Zhen Wei, Meng Ke Zhang, Bai Quan Zhu, Mian Le Xu, Jing Lei, Han Tang, Jun Cai, Yan-Xia Chen
Summary: This study systematically investigates the effect of pH on sulfate adsorption on Pd(111) electrode using cyclic voltammetry. It is found that the onset potential for sulfate adsorption is positively correlated to the solution pH, and in alkaline solutions, sulfate adsorption overlaps with the OHad region. By analyzing the thermodynamic equilibrium potential and the Faradic charge due to adsorption, it is proposed that SO4* is the dominating adsorbate on Pd(111), regardless of whether the main precursor is HSO4- or SO42- in the solution. This has important implications for the understanding of interfacial electrochemical processes, particularly pH-modulated electrochemical reactions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Wenqing Xu, Ying Zheng, Wenhua Yuan, Yongzhong Bao, Guorong Shan, Pengju Pan
Summary: In blends of polymer crystals, amorphous and melted components can segregate into interlamellar or interspherulitic regions. By using a small-molecule liquid crystal probe, different solid phases can be formed at varying PLLA crystallization temperatures, providing a potential way to evaluate spatial segregation in crystallization-induced microphase separation of polymer blends.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Physics, Applied
Timothy E. Kidd, Skylar Scott, Sophie Roberts, Ryan Carlile, Pavel Lukashev, Andrew J. Stollenwerk
Summary: Quantum confinement effects can induce the formation of discrete nanostructures with preferred heights in thin metallic films, with recent discoveries showing that metals grown on van der Waals surfaces can exhibit electronic growth at room temperature. The preferred heights in Pd/MoS2 correlate to the Pd Fermi surface topography and suggest that electronic growth modes are driving factors in the self-assembled Pd nanostructures.
JOURNAL OF APPLIED PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Alisson H. M. da Silva, Georgios Karaiskakis, Rafael E. Vos, Marc T. M. Koper
Summary: This study investigated the formation pathways for hydroxyacetone, acetone, and 1,2-propanediol through CO2 electroreduction. The results showed that ethanol formation occurs through the coupling of CH3* and CO, rather than the glyoxal pathway. For the C-3 compounds, 1,2-propanediol and acetone follow the hydroxyacetone pathway during CO2 electroreduction. This study contributes to a better understanding of the reaction mechanism for these compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Robert Bavisotto, Nicholas Hopper, Alejandro Boscoboinik, Quintus Owen, Wilfred T. Tysoe
Summary: Electron and X-ray diffraction, electron microscopy, and reflection-absorption infrared spectroscopy are used to study the structures of thin organic films on metal substrates. The chemical nature and molecular conformations of the film can be determined from the vibrational frequencies, and the film orientation can be obtained using infrared selection rules. The study on furfural adsorbed on gold and palladium substrates shows that the substrate reactivity influences the film structure, with changes in the furfural film's conformation and order observed with variations in film thickness and temperature.
Article
Chemistry, Multidisciplinary
Yixin Xu, Matheus Dorneles de Mello, Chen Zhou, Shruti Sharma, Burcu Karagoz, Ashley R. Head, Zubin Darbari, Iradwikanari Waluyo, Adrian Hunt, Dario J. Stacchiola, Sergio Manzi, Alejandro M. Boscoboinik, Victor D. Pereyra, J. Anibal Boscoboinik
Summary: A novel material architecture and approach have been used to successfully trap single xenon atoms in silicate nanocages, only releasing them at higher temperatures. The experimental trapping kinetics model proposed has been tested and validated using density functional theory calculations for xenon.
Article
Chemistry, Physical
Chunlei Wang, Yuan Kong, Markus Soldemo, Zongfang Wu, Heloise Tissot, Burcu Karagoz, Kess Marks, Joakim Halldin Stenlid, Andrey Shavorskiy, Esko Kokkonen, Sarp Kaya, Dario J. Stacchiola, Jonas Weissenrieder
Summary: This study presents the synthesis and characterization of a new type of Co1Cu hybrid single-atom catalyst (SAC) on a Cu2O(111) support. The Co1Cu hybrid SACs are found to stabilize the active sites of the Cu2O catalyst and improve its stability under reaction conditions.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Jorge Cored, Mengen Wang, Nusnin Akter, Zubin Darbari, Yixin Xu, Burcu Karagoz, Iradwikanari Waluyo, Adrian Hunt, Dario Stacchiola, Ashley Rose Head, Patricia Concepcion, Deyu Lu, Jorge Anibal Boscoboinik
Summary: Confined nanosized spaces at the interface between a metal and a seemingly inert material can influence the chemistry at the metal surface. This study investigated the effect of doping a silicate with aluminum on the reaction pathway and kinetics of water formation reaction. It was found that introducing aluminum in the bilayer silica increased the residence time of water at the surface, favoring a specific reaction pathway but with a higher energy barrier.
Review
Chemistry, Multidisciplinary
Jennifer D. Lee, Jeffrey B. Miller, Anna Shneidman, Lixin Sun, Jason F. Weaver, Joanna Aizenberg, Juergen Biener, J. Anibal Boscoboinik, Alexandre C. Foucher, Anatoly Frenkel, Jessi E. S. van der Hoeven, Boris Kozinsky, Nicholas Marcella, Matthew M. Montemore, Hio Tong Ngan, Christopher R. O'Connor, Cameron J. Owen, Dario J. Stacchiola, Eric A. Stach, Robert J. Madix, Philippe Sautet, Cynthia M. Friend
Summary: The development of new catalyst materials is crucial for energy-efficient chemical synthesis. Dilute alloy catalysts, which enhance reactivity and retain selectivity, show great promise. The integrated approach, combining materials synthesis, surface chemistry, reaction kinetics, characterization, and theoretical calculations, can predict and improve catalytic selectivity. This approach bridges the gap between fundamental knowledge and the design of complex catalytic systems, leading to the development of new and efficient catalytic processes.
Review
Energy & Fuels
Chenyu Zhou, Zhaoyi Xi, Dario J. Stacchiola, Mingzhao Liu
Summary: Coating or sandwiching an ultrathin layer of TiO2 onto active solar components has been proven as an effective strategy to improve stability and efficiency in solar energy conversion devices. This approach has been widely applied in various types of solar energy conversion devices, showing significant importance.
ENERGY SCIENCE & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Chen Zhou, Hio Tong Ngan, Jin Soo Lim, Zubin Darbari, Adrian Lewandowski, Dario J. Stacchiola, Boris Kozinsky, Philippe Sautet, Jorge Anibal Boscoboinik
Summary: Dynamic restructuring of bimetallic catalysts is crucial for their catalytic activity and selectivity. The authors use CO as a probe and agent to induce surface restructuring in Pd/Au(111) catalysts, uncovering the kinetics and timescale of in situ restructuring. This minute-timescale dynamics provides insights into the fluxional nature of alloy catalysts and the opportunity for surface fine-tuning under moderate conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Fang Xu, Wei An, Ashleigh E. Baber, David C. Grinter, Sanjaya D. Senanayake, Michael G. White, Ping Liu, Dario J. Stacchiola
Summary: Understanding the dynamic processes of hydrogen interaction with oxides is crucial in catalysis. This study investigated the reduction of Cu2O-29 surfaces by hydrogen at room temperature, observing that reduction occurs preferentially at step edges and defects, with the rate depending on nearby Cu step edges. A proposed mechanism involves free copper atoms from ascending metallic step edges facilitating H2 dissociation and transfer to Cu2O regions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Nanoscience & Nanotechnology
Ruoshui Li, Xuance Jiang, Chenyu Zhou, Mehmet Topsakal, Dmytro Nykypanchuk, Klaus Attenkofer, Dario J. Stacchiola, Mark S. Hybertsen, Eli Stavitski, Xiaohui Qu, Deyu Lu, Mingzhao Liu
Summary: This study demonstrates the discovery of structure-property relationships in thin film alloys of complex metal oxides through high-throughput materials synthesis and characterization facilities. Thin films of binary transition metal oxides (Ti-Zn) were prepared with continuously varying Ti:Zn ratio, and the properties of this material family were explored. Spatially resolved techniques such as XANES and XRF were used to probe the atomic structure and electronic properties, and multivariate curve resolution analysis connected the observed properties with the structural and spectral characteristics of crystalline polymorphs of Ti-Zn oxide.
Article
Chemistry, Physical
Jesu's Graciani, David C. Grinter, PedroJ. Ramirez, Robert M. Palomino, Fang Xu, Iradwikanari Waluyo, Dario Stacchiola, Javier Fdez Sanz, Sanjaya Senanayake, Jose A. . Rodriguez
Summary: The surface chemistry of alcohol synthesis from CO2 hydrogenation was investigated over a Pt/CeOx/TiO2 catalyst, which showed high selectivity towards methanol and ethanol. The addition of water promoted the formation of C-C bonds and enhanced the production of ethanol.
Article
Chemistry, Multidisciplinary
Mustafa Karatok, Hio Tong Ngan, Xiwen Jia, Christopher R. O'Connor, J. Anibal Boscoboinik, Dario J. Stacchiola, Philippe Sautet, Robert J. Madix
Summary: Palladium-silver-based alloy catalysts have the potential for CO-free hydrogen production from formic acid. The selective decomposition of formic acid on Pd-Ag alloys was investigated, and it was found that surface Ag domains modified by interaction with subsurface Pd are the key active sites for selective decomposition. In contrast, surface Pd atoms are detrimental to selectivity. The decomposition pathways can be tailored for CO-free H2 production on Pd-Ag alloy systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Liang Chang, Shaoqin Chen, Yuhuan Fei, Dario J. Stacchiola, Yun Hang Hu
Summary: This study achieves a high areal capacitance for supercapacitor electrodes through the synthesis of a new material, providing strategic insights for the rational design of these electrodes.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Physical
Burcu Karagoz, Jennifer Carpena-Nunez, Yi Zhu, Lukas Baker, Klaus Attenkofer, Benji Maruyama, Dario Stacchiola, Dmitri N. Zakharov, Ashley R. Head
Summary: Environmental transmission electron microscopy (ETEM) can monitor structural and chemical changes in nanomaterials under reaction conditions. This study demonstrates the customization of a commercial microheater holder used in ETEM to ambient pressure X-ray photoelectron spectroscopy (APXPS), which allows for the characterization of chemical and electronic structure over larger length scales. The use of the microheaters in APXPS enables fast heating capabilities and subsecond time-resolved spectra collection, providing valuable insights into surface chemical reactions.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Tianhao Hu, Sabrina M. Gericke, Xiao Tong, Dmytro Nykypanchuk, Tove Kristensen, Christian Hulteberg, Dario Stacchiola, Sara Blomberg, Ashley R. Head
Summary: The conversion of biomass to transportation fuels and value-added chemicals is a promising method to reduce the reliance on fossil fuels, and Mo-based catalysts have been shown to be highly active in this process. This study investigates the adsorption behavior of an alumina-supported mixed nickel molybdenum oxide catalyst and finds that molybdenum oxide controls the adsorption and reactivity of the surface species with a cooperative effect by nickel.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Siyuan Fang, Xiao Tong, Dario Stacchiola, Yun Hang Hu
Summary: In this study, we report the formation of solid-state crystals through assembly of the dense HB phosphorous-nitrogen isomers via P···H and P···N bonds and axial D···D interactions. This novel reaction provides a new approach for designing and constructing various molecular crystal materials.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Jesus Graciani, David C. Grinter, Pedro J. Ramirez, Robert M. Palomino, Fang Xu, Iradwikanari Waluyo, Dario Stacchiola, Javier Fdez Sanz, Sanjaya D. Senanayake, Jose A. Rodriguez
Summary: This study investigates the surface chemistry of alcohol synthesis from CO2 hydrogenation over a Pt-CeOx-TiO2 interface. The results show that this interface exhibits excellent catalytic activity for the production of methanol and also generates ethanol. AP-XPS and DFT calculations reveal the active state and the fast pathway for the formation of CH3O species when Ce3+ and Pt are present. Furthermore, the addition of water enhances the CO2 hydrogenation reaction and promotes the formation of C-C bonds, leading to increased ethanol selectivity.
