Article
Chemistry, Multidisciplinary
David C. Grinter, Michael Allan, Hyun Jin Yang, Agustin Salcedo, Gustavo E. Murgida, Bobbie-Jean Shaw, Chi L. Pang, Hicham Idriss, M. Veronica Ganduglia-Pirovano, Geoff Thornton
Summary: A Ce=O terminated ceria surface was observed in this study, revealing a key feature in the reconstruction of ceria islands and potentially shedding light on the unique catalytic properties of ceria-based systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Engineering, Environmental
Ziang Su, Wenzhe Si, Hao Liu, Shangchao Xiong, Xuefeng Chu, Wenhao Yang, Yue Peng, Jianjun Chen, Xingzhong Cao, Junhua Li
Summary: Catalytic combustion is an advanced technology used to eliminate industrial volatile organic compounds. By designing homogeneous interfaces, a mesocrystalline CeO2 catalyst with abundant Ce-Ce homogeneous interfaces was synthesized and showed enhanced catalytic performance for toluene combustion. The abundant Ce-Ce homogeneous interfaces formed by highly ordered stacking and small grain size endow the CeO2 mesocrystal with superior redox property and oxygen storage capacity.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Physical
Jixiang Ji, Ruru Li, Hao Zhang, Yingnan Duan, Qian Liu, Haozhi Wang, Zhurui Shen
Summary: In this study, an Au-CeO2 nanocomposite with Au-O-Ce sites at the micro-interface was developed for the highly selective conversion of CO2 into C2H6. The formation of key intermediates COCO* was confirmed, indicating the role of the Au-CeO2 micro-interface in promoting the multi-electron reduction of CO* and facilitating the production of C2 species. Theoretical calculations suggested that Au-O-Ce sites at the micro-interface could lower the energy barriers for the formation of COOH* and COCO*, resulting in the production of C2H6. The Au-CeO2 nanocomposite exhibited a high C2H6 production rate and electron selectivity.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Physical
Shulan Zhou, Qiang Wan, Sen Lin
Summary: Density functional theory calculations were used to study H-2 dissociation and acetylene hydrogenation on Cu doped CeO2(111). The results showed that Cu doping promotes the formation of oxygen vacancy and creates Cu/O and Ce/O frustrated Lewis pairs. H-2 dissociation proceeds via a heterolytic mechanism with the help of Cu/O frustrated Lewis pair, while C2H2 hydrogenation can be catalyzed by Cu-H and O-H species. Cu doped CeO2(111) exhibits high activity and selectivity for acetylene hydrogenation.
Article
Chemistry, Analytical
Tong Li, Qi Wang, Zhou Wang
Summary: This study investigates the synergistic effect of crystal facets and heavily doped oxygen vacancies in CeO2 nanocrystals. It is found that the most stable CeO2 octahedron with heavily doped (111) facets demonstrates optimal non-enzymatic H2O2 sensing performance, indicating the significant influence of oxygen vacancies on different facets. The inclined distribution states of oxygen vacancies and the electronic transmission property clarify the synergistic effect of facet and oxygen vacancy.
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
Chemistry, Physical
Rajan Singh, Vaibhav Pandey, Kamal Kishore Pant
Summary: This study focuses on the development of Cu/CeO2 catalysts for CO2 conversion to methanol. Different synthesis methods were used to prepare the catalysts, and their performance was evaluated. The results show that the Cu/CeO2 catalyst synthesized by the sol-gel method exhibits superior catalytic properties compared to the co-precipitation method.
Article
Chemistry, Inorganic & Nuclear
Jianping Liu, Guijun Li, Chuanlan Xu, Hongdian Chen, Rong Jin, Lingtao Sun, Chenyang Shu, Haifeng Chen, Chaozhong Guo, Honglin Li, Yujun Si
Summary: A non-noble CeO2/Ce-N-C composite with a hierarchically porous carbon sheet-network structure was synthesized through a supramolecular-gel-pyrolysis (SGP) method. The prepared catalyst exhibited comparable catalytic activity and stability to Pt/C for the oxygen reduction reaction (ORR) in an alkaline electrolyte. The zinc-air battery (ZAB) tests showed higher energy density and better long-term cycling durability. The enhanced ORR activity was attributed to the presence of oxygen vacancies and the Ce-N4O4|CeO2 coupling sites.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Yanan Wei, Yunlei Zhang, Yao Chen, Fang Wang, Yu Cao, Wen Guan, Xin Li
Summary: The concentration of oxygen vacancies on CeO2 crystal faces was found to influence the catalytic activity of the HMF oxidation reaction, with Au nanoparticles showing the highest activity on the CeO2 (110) crystal face. This study provides important insights for the rational design of highly active catalysts for the oxidation of HMF.
Article
Chemistry, Physical
Xueke Zhou, Yang Yang, Jiaben Wang, Weijia Ren, Shaojun Liu, Chenghang Zheng, Xiang Gao
Summary: Precise control of intermediates selectivity in nitrobenzene reduction is a challenging task. By optimizing the defect densities of CeO2 catalysts, the selectivity of azoxybenzene can be improved, with Spindle-structured CeO2 showing a higher nitrobenzene conversion rate but lower azoxybenzene selectivity than Rod-CeO2. Defects in the CeO2 catalysts play a crucial role in catalytic selectivity, where O-vacancy defects act as the main active sites for the reduction process.
APPLIED SURFACE SCIENCE
(2022)
Article
Engineering, Environmental
Meizan Jing, Weiyu Song, Yongfeng Li, Zhen Zhao, Jian Liu, Graeme Henkelman
Summary: Engineering the surface structure of ceira-based catalysts at the atomic scale can significantly enhance their catalytic performance. The current study investigated the structure-activity relationships of Au-CeO2 catalysts with different surfaces, and revealed that defective surfaces promote HCHO oxidation and (110) surface shows the highest activity.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Engineering, Environmental
Meizan Jing, Weiyu Song, Yongfeng Li, Zhen Zhao, Jian Liu, Graeme Henkelman
Summary: Engineering the surface structure of ceria-based catalysts at the atomic scale is a powerful strategy for boosting catalytic performance. Density functional theory calculations show that defective (110) and (100) surfaces of Au-CeO2 catalysts exhibit improved HCHO oxidation performance, with (110) being the most active surface. Microkinetic simulations further support these findings, highlighting the interaction between Au and CeO2 and the effect of different surface terminations on the reactivity for HCHO catalytic oxidation.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Physical
Wenhai Xu, Zhuang Zhang, Hao Sun, Yaning Zhang, Anuj Kumar, Yun Kuang, Yaping Li
Summary: This study investigates the effect of oxygen vacancies and coordinated oxygen on the oxygen evolution reaction by anchoring Ir on various positions of the Co3O4 surface. The results show that coordinated oxygen can modify the electronic structure of Ir, and different positions of Ir have different impacts on the oxygen evolution performance.
Article
Nanoscience & Nanotechnology
Lesia Piliai, Peter Matvija, Thu Ngan Dinhova, Ivan Khalakhan, Tomas Skala, Zdenek Dolezal, Oleksii Bezkrovnyi, Leszek Kepinski, Mykhailo Vorokhta, Iva Matolinova
Summary: In this study, the metal-substrate interaction and species transformation during CO oxidation on CeO2(111) surface were investigated. It was found that the interaction between gold nanoparticles and peroxo oxygen species formed on ceria step edges resulted in the formation of ionic gold species. Moreover, the addition of O2 led to the rapid growth of Au particles and the formation of large particles.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Engineering, Environmental
Shengpeng Mo, Jun Li, Riquan Liao, Peng Peng, Jingjing Li, Junliang Wu, Mingli Fu, Lei Liao, Taiming Shen, Qinglin Xie, Daiqi Ye
Summary: Oxygen vacancy engineering plays a vital role in efficient degradation of volatile organic compounds in nanomaterials. The Pt-0.15Ce-Mn catalyst demonstrates superior catalytic activity for toluene oxidation due to more oxygen vacancies, excellent redox ability, and well dispersion of Pt. Introduction of CeO2 NPs induces the generation of more oxygen vacancies and new structure defects, leading to lower formation energy of oxygen vacancy and boosting remarkable catalytic activity for deep toluene oxidation through a synergistic effect of dual oxygen vacancies.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Physical
Benjamin X. Shi, Venkat Kapil, Andrea Zen, Ji Chen, Ali Alavi, Angelos Michaelides
Summary: In this work, a systematic and general quantum cluster design protocol is proposed to accurately compute the formation energy of oxygen vacancies in metal-oxides. The protocol is applied to rutile TiO2 and rock salt MgO, providing accurate and well-converged determinations of the formation energy. These results are used to benchmark exchange-correlation functionals in density functional theory.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Patrick Rowe, Volker L. L. Deringer, Piero Gasparotto, Gabor Csanyi, Angelos Michaelides
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Andrea Zen, Tai Bui, Tran Thi Bao Le, Weparn J. Tay, Kuhan Chellappah, Ian R. Collins, Richard D. Rickman, Alberto Striolo, Angelos Michaelides
Summary: The aggregation of clay particles in aqueous solution is an important process in both environmental and technological fields. However, the mechanism behind this process at the atomistic level, which involves complex and dynamic interactions such as solvent-mediated electrostatic, hydrogen-bonding, and dispersion interactions, is still poorly understood. In this study, molecular dynamics simulations were conducted to investigate the interactions between kaolinite nanoparticles in pure and salty water. The simulations revealed highly anisotropic behavior, with the interaction between nanoparticles changing from attractive to repulsive depending on their relative orientation. The results of this study highlight the diversity of clay nanoparticle interactions and provide valuable insights for the development of coarse-grained models of clay nanoparticle aggregation.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Ian Y. H. Wu, Stephen J. Jenkins
Summary: The interaction between highly reactive species and solid surfaces can lead to adsorption modes that are different from the typical molecular and dissociative events. This work presents first-principles molecular dynamics calculations that provide insight into the details of abstractive adsorption and highlight the rarity of atomic ejection.
Article
Chemistry, Multidisciplinary
Fabian L. Thiemann, Christoph Schran, Patrick Rowe, Erich A. Muller, Angelos Michaelides
Summary: This study investigates water transport in carbon nanotubes and boron nitride nanotubes using machine learning-based molecular dynamics simulations. The simulations reveal that water experiences less friction on carbon surfaces compared to boron nitride, resulting in faster water flow in carbon nanotubes. The difference in friction arises from different mechanisms, with oxygen motion playing a role in carbon nanotubes and hydrogen-nitrogen interactions in boron nitride nanotubes.
Article
Chemistry, Physical
Sabine C. Matysik, David J. Wales, Stephen J. Jenkins
Summary: Adsorption of chiral molecules on chiral surfaces leads to diastereomerism, resulting in different adsorption geometries. Through first-principles molecular dynamics simulations, we demonstrate that this diastereomerism is reflected in the desorption motion of chiral molecules from a chiral surface. When desorbing from R-Cu{531}, S-Ala molecules show larger angular momentum and a preference for one rotational direction, while R-Ala molecules do not exhibit such preference. These trends are reversed for desorption from S-Cu{531}. Potential applications include chiral separation techniques and enantiospecific sensors.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Anna T. Bui, Fabian L. Thiemann, Angelos Michaelides, Stephen J. Cox
Summary: This article introduces a theoretical framework called "quantum friction" which explains the friction behavior at water-carbon interfaces. Through simulations using a classical model, it is found that the overlap between the solid's dielectric spectrum and water's vibration modes increases friction, supporting the quantum friction theory.
Article
Multidisciplinary Sciences
Alexander Rosu-Finsen, Michael B. Davies, Alfred Amon, Han Wu, Andrea Sella, Angelos Michaelides, Christoph G. Salzmann
Summary: Amorphous ices are important for cosmological processes and understanding liquid water anomalies. A new medium-density amorphous ice (MDA) has been discovered through ball milling ordinary ice Ih at low temperature. This raises the possibility that MDA is the true glassy state of liquid water or a sheared crystalline state. Moreover, the high-energy recrystallization behavior of MDA at low temperature highlights the potential of H2O as a geophysical material.
Article
Chemistry, Multidisciplinary
Cord Bertram, Christopher Zaum, Wei Fang, Angelos Michaelides, Karina Morgenstern
Summary: Solvents have been found to affect chemical reactivity, but the underlying microscopic mechanism is not well understood. This study investigates a model system of water and carbon monoxide on a copper surface using scanning tunneling microscopy and ab initio calculations. The results show that at low temperatures, CO-D2O complexes are more mobile than individual CO or water molecules. The study also provides insights into the detailed mechanism of complex motion. This increase in mobility induced by the solvent could significantly enhance the reaction yield in diffusion-limited surface reactions.
Editorial Material
Multidisciplinary Sciences
C. Richard A. Catlow, Nora H. De Leeuw, Angelos Michaelides, Scott M. Woodley
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES
(2023)
Article
Physics, Multidisciplinary
Christopher Penschke, John Thomas, Cord Bertram, Angelos Michaelides, Karina Morgenstern, Peter Saalfrank, Uwe Bovensiepen
Summary: Understanding the molecular and electronic structure of solvated ions at surfaces requires analyzing the interactions between the surface, ions, and solvent environment. Combining experiment and theory, we investigate the initial stages of Cs+ hydration on a Cu(111) surface and observe inside-out solvation of Cs+ ions at the perimeter of water clusters on the metal surface. Additionally, water-Cs complexes containing multiple Cs+ ions are formed. Established models based on ion-water coordination and conventional solvation cannot explain this, highlighting the importance of understanding the complex microscopic interactions.
PHYSICAL REVIEW LETTERS
(2023)
Article
Materials Science, Multidisciplinary
Yasmine S. Al-Hamdani, Andrea Zen, Angelos Michaelides, Dario Alfe
Summary: Hydrogen plays a crucial role in global efforts to reduce greenhouse gas emissions. Efficient methods of storing hydrogen are needed to make it a widely used fuel. Graphene, a lightweight layered material, has potential for hydrogen storage but currently binds hydrogen too weakly. In this work, we systematically investigate the adsorption of hydrogen on metal-decorated graphene sheets and identify three different mechanisms of binding. We propose that Kubas adsorption, which can be easily manipulated by an external electric field, has potential for tuning hydrogen adsorption. This study enhances our understanding of hydrogen adsorption and lays the foundation for further research.
PHYSICAL REVIEW MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Benjamin X. Shi, Andrea Zen, Venkat Kapil, Peter R. Nagy, Andreas Gruneis, Angelos Michaelides
Summary: The adsorption energy of a molecule on a material surface is crucial for various applications and requires agreement between experimental measurements and theoretical calculations. This study addresses the challenge of accurately predicting the adsorption energy of CO on MgO using advanced computational methods. The inconsistencies in experimental results are explained, leading to reliable theoretical predictions for the design of new catalysts and gas storage materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
John A. Hayton, Michael B. Davies, Thomas F. Whale, Angelos Michaelides, Stephen J. Cox
Summary: The size and growth rate of critical nuclei in thin films of water are minimally affected by the thickness of the film, suggesting that nucleation in films remains similar to bulk water.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Krit Sitathani, Stephen J. Jenkins, Israel Temprano
Summary: In this study, we investigated the adsorption and reaction of NO on the Cu{311} surface using a combination of experimental and theoretical methods. Our results reveal that N2O is formed via the intermediate species N2O2, and the surface is progressively poisoned by the accumulation of oxygen atoms during the reaction. The sustained conversion of NO to N2O on Cu is contingent upon finding a co-reactant capable of continuously removing oxygen from the surface.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)