Review
Engineering, Chemical
Wei-Qi Yan, Yi-An Zhu, Xing-Gui Zhou, Wei-Kang Yuan
Summary: This review summarizes the established scaling relations in heterogeneous catalysis, discusses the strategies for breaking known scaling relations and establishing new generalized scaling relations, and explores the application of machine-learning techniques in catalyst design.
CHINESE JOURNAL OF CHEMICAL ENGINEERING
(2022)
Article
Chemistry, Physical
Xiaoqing Gao, Shanhui Zhu, Mei Dong, Weibin Fan
Summary: By reductive pyrolysis of metal-organic framework precursor, few-layer graphene encapsulated metastable hexagonal closed-packed (hcp) Co nanoparticles were successfully fabricated, showing outstanding performance and stability in converting carboxylic acids to alcohols. Acetic acid undergoes dehydroxylation followed by hydrogenation, with a preference for vertical adsorption on hcp-Co (002) facet, contributing to a decrease in activation barrier during dehydroxylation.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Wenbin Xu, Mie Andersen, Karsten Reuter
Summary: The study identified descriptors using a compressed sensing approach and algebraic expressions to predict adsorption enthalpies of oxygen evolution reaction on metal oxide catalysts, outperforming single descriptors in accuracy and computational cost. Considering features related to local charge transfer significantly improves refined scaling relations, allowing for the screening of OER electrocatalysts with theoretical overpotential uncertainty similar to the expected DFT error.
Article
Nanoscience & Nanotechnology
Azina Rahmani, Maksim A. Sultanov, Kemah Kamiru-White, Lorianne R. Shultz-Johnson, Brian E. Butkus, Shaohua Xie, Fudong Liu, Diep T. H. Nguyen, Noeimie Wilson-Faubert, Ali Nazemi, Parag Banerjee, Lei Zhai, Massimiliano Delferro, Jianguo Wen, Titel Jurca
Summary: Galvanic exchange and atomic layer deposition techniques were used to prepare ultralow loading Pt catalysts with high stability and recyclability. The catalysts showed high activity towards various functionalized styrenes and excellent tolerance towards substituents.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Engineering, Chemical
Ren Feng, Lun Pan, Fengwu Li, Daidi Xu, Ronghui Shi, Libo Dai, Cuicui Ding, Ji-Jun Zou, Min Zhang
Summary: Theoretical investigation of acetylene hydrogenation over FeO, Fe2O3, and Fe3O4 clusters reveals Fe2O3 cluster to have the lowest barriers for the desired reactions, making it the most kinetically favorable for acetylene to ethane hydrogenation process.
CHEMICAL ENGINEERING SCIENCE
(2021)
Article
Chemistry, Physical
Sudarshan Vijay, Georg Kastlunger, Karen Chan, Jens K. Norskov
Summary: Linear scaling relations are important in understanding catalytic activity and selectivity, but not all small molecule adsorbates have linearly scaling chemisorption energies. This study found that the chemisorption energies of carbon and oxygen on transition metal surfaces do not scale due to differences in the re-normalized adsorbate valence energies. A model and a general descriptor were developed to determine if two adsorbates are likely to scale with each other.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Andrea Daru, Carlos Martin-Fernandez, Jeremy N. Harvey
Summary: This article presents a mechanistic investigation of the iron-catalyzed Kumada reaction involving clusters as active species. It suggests that 11- and 13-coordinated clusters are fundamental for initiating the reaction, and proposes a classic initiation step.
Article
Chemistry, Multidisciplinary
Fabio G. Delolo, Johannes Fessler, Helfried Neumann, Kathrin Junge, Eduardo N. Dos Santos, Elena Gusevskaya, Matthias Beller
Summary: A phosphine-oxide-promoted, cobalt-catalysed reductive etherification using syngas as a reductant has been reported in this study. This novel methodology has been successfully applied to prepare unsymmetrical ethers from a wide range of aldehydes and alcohols containing diverse functional groups, and the reaction has been scaled-up to multigram scale under relatively mild conditions. Mechanistic experiments suggest an acetalization-hydrogenation sequence.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Shanhai Zhao, Chunhe Li, Kuankuan Ren, Zebo Fang, Ping Fang, Yanyan Zhu, Pengfei Fang
Summary: In this study, Prussian blue analogs were prepared and calcined to obtain porous transition metal (Ni, Co, Fe) oxides (TMOs). The metal composition of the catalysts significantly influences their structures and catalytic properties. Among them, the NCF-TMO catalyst exhibits excellent photothermal catalytic performance, producing 2.9 mmol g-1 h-1 of CO and 1.6 mmol g-1 h-1 mmol of CH4 at low concentrations of CO2 and H2. The superior catalytic performance of the NCF-TMO catalyst is primarily attributed to the construction of heterojunctions between NiO, Co3O4, and Fe2O3, as well as the formation of abundant surface reactive active sites, facilitating efficient CO2 conversion. This study provides a promising direction for the utilization of CO2 resources.
APPLIED CATALYSIS A-GENERAL
(2023)
Review
Materials Science, Multidisciplinary
Shaima H. Albedwawi, Asala AlJaberi, Gregory N. Haidemenopoulos, Kyriaki Polychronopoulou
Summary: This review highlights the great potential of high entropy oxides (HEO) as promising catalysts compared to conventional metal oxides, emphasizing their superior properties in terms of oxygen activity, oxygen vacancy quantity, and metal dispersion.
MATERIALS & DESIGN
(2021)
Article
Chemistry, Physical
Masa Sterle, Matej Hus, Matic Lozinsek, Anamarija Zega, Andrej Emanuel Cotman
Summary: Stereopure CF3-substituted syn-1,2-diols were synthesized through the reductive dynamic kinetic resolution of corresponding alkyl ketones, yielding products with >95% ee and >87:13 syn/anti ratio. This method provides a rapid access to stereopure bioactive molecules. Moreover, DFT calculations were conducted on three types of Noyori-Ikariya ruthenium catalysts to demonstrate their general ability to control stereoselectivity through hydrogen bond acceptor SO2 region and CH/pi interactions.
Review
Chemistry, Physical
Sarah M. Stratton, Shengjie Zhang, Matthew M. Montemore
Summary: This article discusses the applications of volcano plots and scaling relations in catalyst design and understanding catalytic behavior, and points out the inherent performance limit of catalysts that follow the volcano plot paradigm. It also highlights the materials and design strategies that are not limited by volcano plots and scaling relations.
SURFACE SCIENCE REPORTS
(2023)
Article
Engineering, Environmental
Ying Li, Yunpeng Chen, Zhonglu Guo, Chengchun Tang, Baisheng Sa, Naihua Miao, Jian Zhou, Zhimei Sun
Summary: The group discovered that by substituting a series of TM atoms in Mo3C2 MXene, the catalytic performance of CO2RR can be significantly improved, allowing for the selective reduction of CO2 to methane (CH4) and effectively lowering the limiting potential of the reaction.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Physical
Wouter Stuyck, Aram L. Bugaev, Tom Nelis, Rodrigo de Oliveira-Silva, Simon Smolders, Oleg A. Usoltsev, Daniel Arenas Esteban, Sara Bals, Dimitrios Sakellariou, Dirk De Vos
Summary: In this study, a stable and performant catalyst, Nb2O5.nH(2)O, was found for the production of tricarballylic acid from citric acid. By synthesizing Pd/Nb2O5.nH(2)O catalysts and preserving the acidity of the support using a low temperature reduction method, high yields of tricarballylic acid were obtained. The catalyst also showed suitability for the dehydration-hydrogenation of other monohydroxy carboxylic acids.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Organic
Penglei Cui, Sida Li, Xianjin Wang, Ming Li, Chun Wang, Lipeng Wu
Summary: In this study, the catalytic deaminative alkylation of phosphine compounds was achieved using visible-light photoredox catalysis. The use of Eosin Y as the photoredox catalyst and visible light significantly promoted the reaction, leading to the successful synthesis of a series of unsymmetrical tertiary phosphines, including compounds with three different substituents that are otherwise difficult to obtain.
Article
Nanoscience & Nanotechnology
Evan Z. Carlson, William C. Chueh, J. Tyler Mefford, Michal Bajdich
Summary: The ion insertion redox chemistry of manganese dioxide is widely used in energy storage, catalysis, and chemical separations. This study comprehensively compares the electrochemistry of AxMnO2 (where A = H+, Li+, Na+, K+, Mg2+, Ca2+, Zn2+, Al3+) in aqueous and nonaqueous electrolytes using density functional theory. The selectivity of ion insertion depends on the oxygen coordination environments inside a polymorph for nonprotonic cations, while the presence of H+ usually leads to the formation of hydroxyl bonds. Only three ion-polymorph pairs are thermodynamically stable in aqueous electrolytes, and Al3+ can insert into various polymorphs across the full 2-electron redox of MnO2 at high voltage. These findings provide insights into mixed ion insertion mechanisms in aqueous electrolytes and suggest design strategies for safe and high energy density electrochemical energy storage, desalination batteries, and electrocatalysts.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Jinwon Oh, Arik Beck, Emmett D. Goodman, Luke T. Roling, Anthony Boucly, Luca Artiglia, Frank Abild-Pedersen, Jeroen A. van Bokhoven, Matteo Cargnello
Summary: This study demonstrates that both surface and vapor-mediated ripening occur in distinct temperature regimes, and the sintering mechanism can be altered by adjusting the particle distance. The findings have significant implications for understanding and stabilizing catalysts.
Article
Chemistry, Physical
Karun K. K. Rao, Lan Zhou, Yungchieh Lai, Matthias H. H. Richter, Xiang Li, Yubing Lu, Junko Yano, John M. M. Gregoire, Michal Bajdich
Summary: In this study, the stability and catalytic behavior of Ni-Sb-O oxides for oxygen evolution reaction were investigated. A previously unknown phase was discovered in Ni1-xSbxOz with x > 0.33. Computational simulations and experimental measurements were used to predict and validate the structural and catalytic properties of these oxides. The findings provide valuable insights for the design and optimization of durable and efficient electrode materials for OER.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Wanghui Zhao, Gaomou Xu, Zhaochun He, Cheng Cai, Frank Abild-Pedersen, Tao Wang
Summary: In this study, a new theoretical strategy was proposed to achieve both facile CO dissociation and C/O hydrogenation on a catalyst by introducing confined dual active sites. The DFT-based microkinetic modeling showed that the designed Co-Cr2/G dual-site catalyst provided 4-6 orders of magnitude higher turnover frequency for CH4 production compared to cobalt step sites. We believe that this strategy will provide essential guidance for designing state-of-the-art methanation catalysts under mild conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Xianbiao Fu, Jakob B. Pedersen, Yuanyuan Zhou, Mattia Saccoccio, Shaofeng Li, Rokas Salinas, Katja Li, Suzanne Z. Andersen, Aoni Xu, Niklas H. Deissler, Jon Bjarke Valbaek Mygind, Chao Wei, Jakob Kibsgaard, Peter C. K. Vesborg, Jens K. Norskov, Ib Chorkendorff
Summary: Ammonia is an important substance in various industries and can also be used as a carbon-free fuel. A new approach using lithium-mediated nitrogen reduction has shown promise in the electrochemical synthesis of ammonia. In this study, a continuous-flow electrolyzer with gas diffusion electrodes was used, and a platinum-gold alloy catalyst was found to be more stable and efficient for the reaction. The results showed a high faradaic efficiency for ammonia production and energy efficiency at optimal conditions.
Article
Multidisciplinary Sciences
Hemanth Somarajan Pillai, Yi Li, Shih-Han Wang, Noushin Omidvar, Qingmin Mu, Luke E. K. Achenie, Frank Abild-Pedersen, Juan Yang, Gang Wu, Hongliang Xin
Summary: This study uses quantum chemistry and machine learning to understand the reaction mechanism and design efficient electrocatalysts for the electrochemical conversion of ammonia to nitrogen. By training graph neural networks on ab initio data, the authors explore the design space of ternary Pt alloy nanostructures and predict site reactivity, surface stability, and catalyst synthesizability. The machine-learned representation of site motifs provides important insights into chemical bonding at metal surfaces and guides the design of high-performance catalytic systems.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Lingze Wei, Md Delowar Hossain, Michael J. Boyd, Jaime Aviles-Acosta, Melissa E. Kreider, Adam C. Nielander, Michaela Burke Stevens, Thomas F. Jaramillo, Michal Bajdich, Christopher Hahn
Summary: The electrochemical conversion of benzyl alcohol to benzaldehyde and benzoate was investigated on nickel-iron electrodes. The study showed that the oxidation onset of benzyl alcohol is strongly correlated to the redox properties of nickel ions, especially Ni3+. The incorporation of iron into the system also affects the redox position and oxidation onset. Density functional theory calculations provided insights into the mechanism and showed the possibility of a vacancy-driven mechanism.
Article
Chemistry, Physical
Ang Cao, Jens K. Norskov
Summary: Using density functional theory calculations, this work demonstrates that controlling the spin state of magnetic metal surfaces significantly impacts their chemical properties. The adsorption energy of various adsorbates is shown to be stronger on non-spin polarized surfaces compared to spin polarized ground state surfaces. This finding is consistent for Fe, Co, and Ni surfaces, as well as three commonly used exchange-correlation functionals. The origin of this effect is discussed in terms of surface electronic structure, and a simple model based on the d-band model of adsorption is proposed to explain the phenomenon. The study also explores the potential of utilizing spin effects to manipulate surface reactivity, such as through the addition of a metal promotor.
Article
Materials Science, Multidisciplinary
Hirohito Ogasawara, Han Wang, Jorgen Gladh, Alessandro Gallo, Ralph Page, Johannes Voss, Alan Luntz, Elias Diesen, Frank Abild-Pedersen, Anders Nilsson, Markus Soldemo, Marc Zajac, Andrew Attar, Michelle E. Chen, Sang Wan Cho, Abhishek Katoch, Ki-Jeong Kim, Kyung Hwan Kim, Minseok Kim, Soonnam Kwon, Sang Han Park, Henrique Ribeiro, Sami Sainio, Hsin-Yi Wang, Cheolhee Yang, Tony Heinz
Summary: We conducted optical pumping and x-ray absorption spectroscopy experiments on a graphene monolayer adsorbed on copper using a free electron laser. Our analysis suggests that the excitation of graphene is primarily due to indirect excitation from hot electron-hole pairs created in the copper. However, once the excitation occurs in graphene, its decay follows a similar path as in previous studies of graphene adsorbed on semiconductors, involving rapid excitation of strongly coupled optical phonons and eventual thermalization. The lifetime of the hot electron-hole pairs in copper likely influences the lifetime of the electronic excitation in graphene.
PHYSICAL REVIEW MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Naiwrit Karmodak, Jens K. Norskov
Summary: In this study, a computational catalyst-screening method was designed to identify potentially interesting single-atom catalysts (SACs) and di-atom catalysts (DACs) for the O-2 reduction reaction (ORR). Four SACs and fifteen DACs with high estimated catalytic activity were identified, some of which showed high stability in both acidic and alkaline media.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Viswanath Pasumarthi, Henry Yu, Sneha A. Akhade, Frank Abild-Pedersen, Joel B. Varley, Michal Bajdich
Summary: Solvation models are important for understanding electrochemical reactions. This study developed a framework to evaluate the effects of potential and electrical double layer on CO reduction. Different solvation models were compared and good agreement was found for intermediate products. This framework can be used to predict optimal electrochemical conditions for specific applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Multidisciplinary Sciences
Jihyun Baek, Md Delowar Hossain, Pinaki Mukherjee, Junghwa Lee, Kirsten T. Winther, Juyoung Leem, Yue Jiang, William C. Chueh, Michal Bajdich, Xiaolin Zheng
Summary: Developing stable and efficient electrocatalysts is crucial for enhancing oxygen evolution reaction rates in sustainable hydrogen production. This study investigates the activity and stability of high-entropy spinel oxides with element mixing and strains using theoretical and experimental approaches, revealing their superior performance.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Shyama Charan Mandal, Frank Abild-Pedersen
Summary: The design of heterogeneous catalysts can be accelerated by identifying relevant descriptors that link binding and activation energies to reactivity. This study investigated scaling relations between binding energies of various hydrocarbon-based adsorbates on different Pt surfaces and metal binding energies estimated via the alpha-scheme model. The findings show that the binding energies of certain groups of adsorbates can be used to predict the binding energies of more complex hydrocarbon-based adsorbates.
Article
Chemistry, Physical
Joakim Halldin Stenlid, Verena Streibel, Tej Salil Choksi, Frank Abild-Pedersen
Summary: Bimetallic alloys are important catalytic materials with various shapes, sizes, and compositions. Predicting catalytic turnovers of individual active sites is challenging due to the combinatorics across this materials space. This study introduces site stability as a descriptor for site-resolved reaction rates, which unifies structural and compositional variations. By using coordination-based models trained with density functional theory (DFT) calculations, instantaneous predictions of catalytic turnovers for nanostructures up to 12 nm in size are conducted. By identifying stable active sites on AuPt nanoparticles, higher reaction rates than monometallic Pt are achieved. This method guides the design of bimetallic catalysts with optimal turnovers through specific sizes, morphologies, and compositions of nanoparticles.
