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| Open AccessAnharmonic quantum nuclear densities from full dimensional vibrational eigenfunctions with application to protonated glycine
Accurate interpretation of molecular vibrational spectroscopic signals is key to understand chemical processes. Here the authors introduce a new computational approach to represent vibrational modes in terms of nuclear densities that captures anharmonic effects in protonated glycine.
- Chiara Aieta
- , Marco Micciarelli
- & Michele Ceotto
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Article
| Open AccessExcess-entropy scaling in supercooled binary mixtures
Supercooled liquids near the glass transition show remarkable non-Arrhenius transport phenomena, whose origin is yet to be clarified. Here, the authors use GPU molecular dynamics simulations for various binary mixtures in the supercooled regime to show the validity of a quasiuniversal excess-entropy scaling relation for viscosity and diffusion.
- Ian H. Bell
- , Jeppe C. Dyre
- & Trond S. Ingebrigtsen
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Article
| Open AccessModulating oxygen coverage of Ti3C2Tx MXenes to boost catalytic activity for HCOOH dehydrogenation
Developing non-noble-metal heterogeneous catalysts with high efficiency in HCOOH dehydrogenation is significant for the acquisition of hydrogen, but remains a great challenge. Here, the authors modulate oxygen coverage of Ti3C2Tx MXenes to boost the catalytic activity toward HCOOH dehydrogenation.
- Tingting Hou
- , Qiquan Luo
- & Liangbing Wang
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Article
| Open AccessLattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation
Electrocatalytic water oxidation is facilitated by high valence states, but these are challenging to achieve at low applied potentials. Here, authors report a multicomponent FeCoCrNi alloy with dynamically formed Ni4+ species to offer high catalytic activity via lattice oxygen activation mechanism.
- Ning Zhang
- , Xiaobin Feng
- & Yang Chai
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Article
| Open AccessObservation of the geometric phase effect in the H+HD→H2+D reaction below the conical intersection
The geometric phase effect associated with a conical intersection between the ground and first excited electronic state has been predicted in the H3 system below the conical intersection energy. The authors, by a crossed molecular beam technique and quantum dynamic calculations, provide experimental evidence and insight into its origin.
- Daofu Yuan
- , Yin Huang
- & Xueming Yang
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Article
| Open AccessAutomated extraction of chemical synthesis actions from experimental procedures
Extracting experimental operations for chemical synthesis from procedures reported in prose is a tedious task. Here the authors develop a deep-learning model based on the transformer architecture to translate experimental procedures from the field of organic chemistry into synthesis actions.
- Alain C. Vaucher
- , Federico Zipoli
- & Teodoro Laino
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Article
| Open AccessMachine learning accurate exchange and correlation functionals of the electronic density
Increasing the non-locality of the exchange and correlation functional in DFT theory comes at a steep increase in computational cost. Here, the authors develop NeuralXC, a supervised machine learning approach to generate density functionals close to coupled-cluster level of accuracy yet computationally efficient.
- Sebastian Dick
- & Marivi Fernandez-Serra
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Article
| Open AccessA flat carborane with multiple aromaticity beyond Wade–Mingos’ rules
The polyhedral skeletal electron pair theory (PESPT), also known as Wade-Mingos’ rules, defines a relationship between skeletal bonding electron pairs and structure of clusters. Here the authors report the synthesis, structure and computational studies of planar C2B4R4 carboranes that do not adhere to PESPT.
- Wei Lu
- , Dinh Cao Huan Do
- & Rei Kinjo
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Article
| Open AccessDe novo design of Au36(SR)24 nanoclusters
The discovery of atomically precise metal nanoclusters is generally unpredictable, and there are few examples of their rational synthesis. Here, the authors report the de novo design of Au36(SR)24 nanoclusters, from theoretical prediction to experimental synthesis and characterization of physicochemical properties.
- Xu Liu
- , Wen Wu Xu
- & Yan Zhu
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Article
| Open AccessCharacterization of an alternative BAK-binding site for BH3 peptides
Mitochondrial apoptosis is controlled by BCL2 family proteins, and the BH3-only proteins often act as sensors that transmit apoptotic signals. Here the authors show how the BH3-only proteins BMF and HRK can directly activate the BCL2 protein BAK and interact with BAK through an alternative binding groove.
- Kaiqin Ye
- , Wei X. Meng
- & Haiming Dai
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Article
| Open Accessπ covalency in the halogen bond
Current models of halogen bonding describe the σ-symmetric component of this interaction but do not contemplate the possibility of π-covalency. Here the authors provide experimental and computational evidence of π-covalency in halogen bonds involving radical cation halogen bond donors.
- Cameron W. Kellett
- , Pierre Kennepohl
- & Curtis P. Berlinguette
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Article
| Open AccessUncovering the effects of interface-induced ordering of liquid on crystal growth using machine learning
Crystallization is a challenging process to model quantitatively. Here the authors use machine learning and atomistic simulations together to uncover the role of the liquid structure on the process of crystallization and derive a predictive kinetic model of crystal growth.
- Rodrigo Freitas
- & Evan J. Reed
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Article
| Open AccessRepresentation of molecular structures with persistent homology for machine learning applications in chemistry
The choice of molecular representations can severely impact the performances of machine-learning methods. Here the authors demonstrate a persistence homology based molecular representation through an active-learning approach for predicting CO2/N2 interaction energies at the density functional theory (DFT) level.
- Jacob Townsend
- , Cassie Putman Micucci
- & Konstantinos D. Vogiatzis
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Article
| Open AccessTuning reactivity of Fischer–Tropsch synthesis by regulating TiOx overlayer over Ru/TiO2 nanocatalysts
The activity of Fischer–Tropsch synthesis (FTS) can be promoted by the reducible oxides, while their role remains elusive. Here, the authors reveal that, by varying the reduction condition to regulate the TiOx overlayer on Ru nanocatalysts, the TiOx overlayer participate in the C–O bond dissociation.
- Yaru Zhang
- , Xiaoli Yang
- & Tao Zhang
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Article
| Open AccessDissociation of salts in water under pressure
Salts in water at extreme conditions play a fundamental role in determining the properties of the Earthʼs mantle constituents. Here the authors shed light on ion-water and ion-ion interactions for NaCl dissolved in water at conditions relevant to the Earthʼs upper mantle by molecular dynamics simulations.
- Cunzhi Zhang
- , Federico Giberti
- & Giulia Galli
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Article
| Open AccessMultisecond ligand dissociation dynamics from atomistic simulations
Protein-ligand unbinding processes are out of reach for atomistic simulations due to time-scale involved. Here the authors demonstrate an approach relying on dissipation-corrected targeted molecular dynamics that enables to provide binding and unbinding rates with a speed-up of several orders of magnitude.
- Steffen Wolf
- , Benjamin Lickert
- & Gerhard Stock
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Article
| Open AccessSynthesis and versatile reactivity of scandium phosphinophosphinidene complexes
Rare-earth monometallic phosphinidene complexes have been elusive synthetic targets. Here, the authors describe the synthesis and tunable reactivity of two scandium phosphinophosphinidene complexes containing very unusual Sc-P multiple bonds.
- Bin Feng
- , Li Xiang
- & Yaofeng Chen
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Article
| Open AccessCharacterization of glycosyl dioxolenium ions and their role in glycosylation reactions
Dioxolenium ion intermediates formed from remote positions are hypothesized to direct stereoselective glycosylations. Herein we combine infrared ion spectroscopy, DFT calculations and synthetic work to characterize and study these dioxolenium ions and their role in stereoselective glycosylation reactions.
- Thomas Hansen
- , Hidde Elferink
- & Thomas J. Boltje
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Article
| Open AccessComputer simulations explain the anomalous temperature optimum in a cold-adapted enzyme
Enzymes from organisms inhabiting cold environments (psychrophiles) have adapted to catalyzing chemical reactions at near freezing temperatures. Here – using molecular dynamics simulations – the authors analyze cold adaptation of psychrophilic α-amylase and provide the structural basis for its low anomalous temperature optimum: the increased mobility of a surface loop involved in substrate interaction.
- Jaka Sočan
- , Miha Purg
- & Johan Åqvist
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Article
| Open AccessMolecular molds for regularizing Kondo states at atom/metal interfaces
The surrounding environment’s influence on the Kondo states formed around an adsorbed transition metal atom are challenging potential applications. Here, the authors demonstrate, via STM and DFT+HEOM calculations, that a metal phthalocyanine molecule on an Au(111) surface enables a fine tuning of the Kondo characteristics.
- Xiangyang Li
- , Liang Zhu
- & Jinlong Yang
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Article
| Open AccessIn-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution
NiFe and CoFe layered double hydroxides are among the most active electrocatalysts for the alkaline oxygen evolution reaction. Here, by combining operando experiments and rigorous DFT calculations, the authors unravel their active phase, the reaction center and the catalytic mechanism.
- Fabio Dionigi
- , Zhenhua Zeng
- & Peter Strasser
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Article
| Open AccessSelective electroreduction of CO2 to acetone by single copper atoms anchored on N-doped porous carbon
Efficient electroreduction of CO2 to multi-carbon products is challenging. Here, the single atom Cu encapsulated on N-doped porous carbon catalysts are designed for reducing CO2 to acetone at low overpotentials and the active sites are identified as Cu coordination with four pyrrole-N atoms.
- Kun Zhao
- , Xiaowa Nie
- & Jingguang G. Chen
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Article
| Open AccessFermionic neural-network states for ab-initio electronic structure
Despite the importance of neural-network quantum states, representing fermionic matter is yet to be fully achieved. Here the authors map fermionic degrees of freedom to spin ones and use neural-networks to perform electronic structure calculations on model diatomic molecules to achieve chemical accuracy.
- Kenny Choo
- , Antonio Mezzacapo
- & Giuseppe Carleo
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Article
| Open AccessTransient-axial-chirality controlled asymmetric rhodium-carbene C(sp2)-H functionalization for the synthesis of chiral fluorenes
The formation of chiral molecules generally relies on direct chirality transfer from catalyst to products. Here, the authors report a strategy based on point chirality transfer from the catalyst to a dirhodium carbene intermediate with axial chirality, which is then transferred to products via C(sp2)-H functionalization.
- Kuiyong Dong
- , Xing Fan
- & Xinfang Xu
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Article
| Open AccessPrediction of organic homolytic bond dissociation enthalpies at near chemical accuracy with sub-second computational cost
Bond dissociation enthalpies are key quantities in determining chemical reactivity, their computations with quantum mechanical methods being highly demanding. Here the authors develop a machine learning approach to calculate accurate dissociation enthalpies for organic molecules with sub-second computational cost.
- Peter C. St. John
- , Yanfei Guan
- & Robert S. Paton
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Article
| Open AccessBuilding and identifying highly active oxygenated groups in carbon materials for oxygen reduction to H2O2
The identity of catalytic sites for H2O2 generation in carbon-based materials remains controversial with limited experimental evidence to date. Here, the authors decorate various target functional groups on carbon materials and quinone-enriched samples exhibit the highest activity and selectivity.
- Gao-Feng Han
- , Feng Li
- & Jong-Beom Baek
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Article
| Open AccessLipid-protein interactions modulate the conformational equilibrium of a potassium channel
Potassium (K+) channels, such as MthK, are essentional for many biological processes, but how lipid-protein interactions regulate ion permeation of K+ channels remained unclear. Here authors conducted molecular dynamics simulations of MthK and observed different ion permeation rates of MthK in membranes with different properties.
- Ruo-Xu Gu
- & Bert L. de Groot
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Article
| Open AccessObservation of the molecular response to light upon photoexcitation
Photoabsorption is a fundamental process that leads to changes in the electron density in matter. Here, the authors show a direct measurement of the distribution of electron density when a cyclohexadine molecule is excited by pulsed UV radiation and probed by a time delayed X-ray pulse generated at LCLS.
- Haiwang Yong
- , Nikola Zotev
- & Peter M. Weber
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Article
| Open AccessAutonomous discovery of optically active chiral inorganic perovskite nanocrystals through an intelligent cloud lab
Synthetic platforms coupled with artificial intelligent algorithms are highly desirable for advancing the discovery of new materials with target properties. Here the authors demonstrate the use of an autonomous laboratory for the discovery of optically active CsPbBr3 inorganic perovskite nanocrystals.
- Jiagen Li
- , Junzi Li
- & Xi Zhu
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Article
| Open AccessVoltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
Determining catalyst electronic structures during electrochemical reactions is crucial to understand mechanisms. Here authors perform in operando soft X-ray spectroscopy on a cobalt oxide catalyst during O2 evolution and observe voltage and time-dependent valence state transitions.
- Jing Zhou
- , Linjuan Zhang
- & Zhiwei Hu
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Article
| Open AccessUnusual KIE and dynamics effects in the Fe-catalyzed hetero-Diels-Alder reaction of unactivated aldehydes and dienes
Recently an iron catalyst was developed to catalyze an oxa-Diels-Alder reaction, whose mechanism is unclear yet. Here the authors combine DFT and molecular dynamics simulations with experimental studies to elucidate the unusual iron effect on kinetic isotope effect and dynamics in this reaction.
- Yuhong Yang
- , Xiaoyong Zhang
- & Lung Wa Chung
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Article
| Open AccessQuantitative prediction of grain boundary thermal conductivities from local atomic environments
Connecting grain boundary structures to macroscopic thermal behaviour is an important step in materials analysis and design. Here the authors develop a physical model combined with a machine-learning approach to accurately predict thermal conductivities of various types of MgO grain boundaries.
- Susumu Fujii
- , Tatsuya Yokoi
- & Masato Yoshiya
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Article
| Open AccessFrom quantum to continuum mechanics in the delamination of atomically-thin layers from substrates
The unexpectedly long-ranged interface stress observed in recent delamination experiments is yet to be clarified. Here, the authors develop an analytical approach to show the wavelike atomic deformation as the origin for the observed ultra long-range stress in delamination of graphene from various substrates.
- Paul Hauseux
- , Thanh-Tung Nguyen
- & Alexandre Tkatchenko
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Article
| Open AccessOrigins of fast diffusion of water dimers on surfaces
The experimental observation that water dimers diffuse more rapidly than monomers across materials’ surfaces is yet to be clarified. Here the authors show by ab initio calculations classical and quantum mechanical mechanisms for faster water dimer diffusion on a broad range of metal and non-metal surfaces.
- Wei Fang
- , Ji Chen
- & Angelos Michaelides
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Article
| Open AccessStructure and chemistry of graphene oxide in liquid water from first principles
Graphene oxide holds great promise for water purification applications, though its chemical reactivity in water is yet to be clarified. Here the authors show by first principles molecular dynamics that graphene oxide structures with correlated functional groups and regions of pristine graphene are the most stable in liquid water.
- Félix Mouhat
- , François-Xavier Coudert
- & Marie-Laure Bocquet
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Article
| Open Accessδ and φ back-donation in AnIV metallacycles
Metal-ligand δ and φ interactions, though considered weak, may be necessary for fully describing the electronic and geometric structures of certain compounds. Here, in actinide metallacycles, the authors discover two new types of M-L δ and φ back-bonds that contribute substantially to their unusual chemical behavior.
- Morgan P. Kelley
- , Ivan A. Popov
- & Ping Yang
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Article
| Open AccessTRIM5α self-assembly and compartmentalization of the HIV-1 viral capsid
Tripartite-motif containing (TRIM) proteins modulate cellular responses to viral infection. Here the authors use molecular dynamics simulations to demonstrate that TRIM5α uses a two-dimensional lattice hopping mechanism to aggregate on the HIV capsid surface and initiate lattice growth.
- Alvin Yu
- , Katarzyna A. Skorupka
- & Gregory A. Voth
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Article
| Open AccessThe electronic structure of benzene from a tiling of the correlated 126-dimensional wavefunction
The electronic structure of benzene has been a test bed for competing theories along the years. Here the authors show via quantum chemistry calculations that the wavefunction of benzene can be partitioned into tiles which show that the two electron spins exhibit staggered Kekulé structures.
- Yu Liu
- , Phil Kilby
- & Timothy W. Schmidt
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Article
| Open AccessHigh-efficiency direct methane conversion to oxygenates on a cerium dioxide nanowires supported rhodium single-atom catalyst
Direct methane conversion to high value-added products is a promising way for highly-efficient utilization of methane. Here, the authors demonstrate that rhodium single-atom supported on cerium dioxide nanowires can selectively convert methane to oxygenates under mild conditions.
- Shuxing Bai
- , Fangfang Liu
- & Xiaoqing Huang
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Article
| Open AccessCharge transfer as a ubiquitous mechanism in determining the negative charge at hydrophobic interfaces
The accumulation of negative charge at hydrophobic–water interfaces has been a source of debate for a long time. Here the authors use ab initio calculations to show that the charge accumulation at air–water and oil–water interfaces is caused by subtle charge transfer processes.
- Emiliano Poli
- , Kwang H. Jong
- & Ali Hassanali
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Article
| Open AccessArtificial relativistic molecules
Artificial molecules supported on templated surfaces attract enormous interest due to their tunable electronic properties. Here the authors use STM experiments and DFT calculations to show the formation of Pb artificial clusters on a IrTe2 honeycomb template that are maximally stabilized by relativistic effects.
- Jae Whan Park
- , Hyo Sung Kim
- & Han Woong Yeom
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Article
| Open AccessCharge transfer from the carotenoid can quench chlorophyll excitation in antenna complexes of plants
The plant photosynthetic machinery quenches excess excitation energy to avoid photodamage. Here, via molecular dynamics and quantum chemical calculations, Cupellini et al. show that lutein/chlorophyll pairs in light-harvesting complex II can quench excess energy via a transient charge transfer state.
- Lorenzo Cupellini
- , Dario Calvani
- & Benedetta Mennucci
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Article
| Open AccessA first principles method to determine speciation of carbonates in supercritical water
The determination of the speciation of ions and molecules in supercritical aqueous fluids under pressure is key to understanding their mass transport in the Earth’s interior. Here the authors present a strategy based on ab-initio molecular dynamics to determine the speciation of carbonates in aqueous fluids.
- Ding Pan
- & Giulia Galli
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Article
| Open AccessInterplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold
Supramolecular catalytic assemblies attract enormous interest due to their activity that rivals natural enzymes. Using ab initio molecular dynamics, the authors show that a gold catalyst in a Ga4L612- nanocage, while impeded by reorganization energy, is accelerated by hosting a catalytic water molecule.
- Valerie Vaissier Welborn
- , Wan-Lu Li
- & Teresa Head-Gordon
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Article
| Open AccessReaction scope and mechanistic insights of nickel-catalyzed migratory Suzuki–Miyaura cross-coupling
Migratory cross-coupling reactions are powerful tools to form bonds at predictable positions. Here the authors report a nickel-catalyzed migratory Suzuki–Miyaura cross-coupling of unactivated alkyl electrophiles with aryl and vinyl boron reagents and provide experimental and computational mechanistic evidence.
- Yuqiang Li
- , Yixin Luo
- & Guoyin Yin
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Article
| Open AccessFeshbach resonances in the F + H2O → HF + OH reaction
Feshbach resonances are transiently trapped states along a reaction coordinate, providing a probe to the reaction’s potential energy surface (PES) but difficult to analyze in polyatomic systems. Here the authors identify Feshbach resonances in a reacting 4-atom system by state-to-state quantum dynamics using a full-dimensional PES.
- Xiaoren Zhang
- , Lulu Li
- & Dong H. Zhang
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Article
| Open AccessRealization of Lieb lattice in covalent-organic frameworks with tunable topology and magnetism
Although artificial Lieb lattices have been recently synthesized, the realization of a Lieb lattice in a real material is still challenging. Here the authors use tight-binding and first principle calculations to predict tunable topology and magnetism in recently discovered two-dimensional covalent-organic frameworks.
- Bin Cui
- , Xingwen Zheng
- & Bing Huang
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Article
| Open AccessAmorphization activated ruthenium-tellurium nanorods for efficient water splitting
Elctrochemical water splitting is of vital significance for energy conversion and storage. Here the authors show an electrocatalyst based on amorphous ruthenium-tellurium porous nanorods which exhibit significantly improved OER performance than its crystalline counterparts
- Juan Wang
- , Lili Han
- & Xiaoqing Huang
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Article
| Open AccessPalladium-bearing intermetallic electride as an efficient and stable catalyst for Suzuki cross-coupling reactions
In Suzuki coupling reactions, excellent catalytic performance require negatively charged Pd species and the avoidance of metal leaching or clustering. Here the authors implanted Pd sites into an intermetallic electride, Y3Pd2, which serves as an efficient and stable catalyst for Suzuki coupling reactions.
- Tian-Nan Ye
- , Yangfan Lu
- & Hideo Hosono