Converting earth-abundant dinitrogen into value-added chemical ammonia is a significant yet challenging topic. Electrocatalytic nitrogen reduction reaction (NRR), compared with conventional Haber-Bosch process, is an energy-saving and environmentally friendly approach. The major task of electrocatalytic NRR is to find electrocatalysts which can activate dinitrogen effectively and exhibit high selectivity and stability. Single atom catalysts can act as a good solution. In this work, by means of first-principles density functional theory, molecular dynamics calculations, and a two-step screening process, we confirm that single Sc and Ti atom supported on tetracyanoquinodimethane monolayers (Sc,Ti-TCNQ) are excellent candidates for NRR electrocatalysts. N2 adsorption and activation are effective due to the acceptance-donation mechanism and outstanding electronic structure of TM-TCNQ, and Gibbs free energy diagram shows that Sc-TCNQ and Ti-TCNQ exhibit low NRR overpotential of 0.33 and 0.22 V through enzymatic-consecutive mixed pathway, respectively. In addition, selectivity over HER and stability of Sc/Ti-TCNQ monolayers are also validated. This work opens a new avenue for designing novel single atom catalysts for NRR as well as other catalytic applications.
Pt/Graphene and Pt/MnO2-Graphene catalysts have been prepared by microwave-assisted polyol process. Electrochemical results show that Pt/MnO2-Graphene has higher electrocatalytic activity and stability. Furthermore, carbon riveted Pt/MnO2-Graphene catalyst has been designed and synthesized on the basis of in situ carbonization of L-ascorbic acid. The stability for carbon riveted Pt/MnO2-catalyst is significantly enhanced.
The Key Steps and Distinct Performance Trends of Pyrrolic vs. Pyridinic M-N-C Catalysts in Electrocatalytic Nitrate Reduction
Advanced Institute for Materials Research (WPI-AIMR), Tohoku University（东北大学物质材料研究创新世界首脑研究所）；School of Chemical and Biomolecular Engineering, The University of Sydney（悉尼大学化学与生物分子工程学院）；State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences（中国科学院长春应用化学研究所稀土资源利用国家重点实验室）；School of Applied Chemistry and Engineering, University of Science and Technology of China（中国科学技术大学应用化学与工程学院）
Renewable energy conversion and storage, and greenhouse gas emission-free technologies are within the primary tasks and challenges for the society. Hydrogen fuel, produced by alkaline water electrolysis is fulfilling all these demands, however the technology is economically feeble, limited by the slow rate of oxygen evolution reaction. Complex metal oxides were suggested to overcome this problem being low-cost efficient catalysts. However, the insufficient long-term stability, degradation of structure and electrocatalytic activity are restricting their utilization. Here we report on a new pero…
Free-Energy Analysis of Bubble Nucleation on Electrocatalytic Surfaces
Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Forschungszentrum Jülich（亥姆霍兹尤利希埃尔朗根可再生能源研究所）；Friedrich-Alexander-Universität Erlangen-Nürnberg（埃尔朗根-纽伦堡弗里德里希·亚历山大大学）
The four-electron oxygen reduction reaction on Pt catalyst in alkaline solution undergoes proton transfer via tunneling mechanism. The hydrogen/deuterium kinetic isotopic rate constant ratio (kH/kD ) = 32 in a low overpotential region, indicating the importance of the quantum-proton-tunneling at the rate-determining step (RDS). However, kH/kD goes down to 3 in a high overpotential region, suggesting the classical proton-transfer (PT) scheme. Therefore, there is a quantum-to-classical transition of PT process as a function of potential, which is confirmed by theoretical study.
Electrocatalysts for bifunctional oxygen reduction (ORR) and oxygen evolution reaction (OER) are commonly studied under hydrodynamic conditions, rendering the use of binders necessary to ensure the mechanical stability of the electrode films. The presence of a binder, however, may influence the properties of the materials under examination to an unknown extent. Herein, we investigate the impact of Nafion on a highly active ORR/OER catalyst consisting of MnFeNi oxide nanoparticles supported on multi-walled carbon nanotubes. Electrochemical studies revealed that, in addition to enhancing the mec…
Active, selective and stable catalysts are imperative for sustainable energy conversion, and engineering materials with such properties are highly desired. High-entropy alloys (HEAs) offer a vast compositional space for tuning such properties. Too vast, however, to traverse without the proper tools. Here, we report the use of Bayesian optimization on a model based on density functional theory (DFT) to predict the most active compositions for the electrochemical oxygen reduction reaction (ORR) with the least possible number of sampled compositions for the two HEAs Ag-Ir-Pd-Pt-Ru and Ir-Pd-Pt-Rh…
Electrocatalytic hydrogen evolution reaction (HER) in alkaline media is a promising electrochemical energy conversion strategy. Ruthenium (Ru) is an efficient catalyst with a desirable cost for HER, however, the sluggish H2O dissociation process, due to the low H2O adsorption on its surface, currently hampers the performances of this catalyst in alkaline HER. Herein, we demonstrate that the H2O adsorption improves significantly by the construction of Ru-O-Mo sites. We prepared Ru/MoO2 catalysts with Ru-O-Mo sites through a facile thermal treatment process and assessed the creation of Ru-O-Mo i…
A novel oxygen evolution reaction (OER) catalyst (3D S235-P steel) based on steel S235 substrate has been successfully prepared via a facile one-step surface modification. The standard Carbon Manganese steel was phosphorizated superficially leading to the formation of a unique 3D interconnected nanoporous surface with high specific area which facilitates the electrocatalytically initiated oxygen evolution reaction. The prepared 3D S235-P steel exhibits enhanced electrocatalytic OER activities in alkaline regime confirmed by a low overpotential (η=326 mV at j=10 mA cm-2) and a small Tafel slope…
Designing electrocatalysts for HER in alkaline conditions to overcome the sluggish kinetics associated with the additional water dissociation step is a recognized challenge in promoting the hydrogen economy. To this end, delicately tuning the atomic-scale structure and surface composition of nanoparticles is a common strategy and, specifically, making use of hybrid structures, can produce synergistic effects that lead to highly active catalysts. Here, we present a core-shell catalyst of Ag@MoS$_2$ that shows promising results towards the hydrogen evolution reaction (HER) in both 0.5 M H2SO4 an…
Catalysis distillation neural network for the few shot open catalyst challenge
Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology（广西石化资源加工及过程强化技术重点实验室）；School of Chemistry and Chemical Engineering, Guangxi University（广西大学化学化工学院）
The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet under…
Prediction of CO2 reduction reaction intermediates and products on transition metal-doped r-GeSe monolayers:A combined DFT and machine learning approach
Synthesis of ammonia through photo- and electrocatalysis is a rapidly growing field. Titania-based catalysts are widely reported for photocatalytic ammonia synthesis and have also been suggested as electrocatalysts. The addition of transition-metal dopants is one strategy for improving the performance of titania-based catalysts. In this work, we screen d-block transition-metal dopants for surface site stability and evaluate trends in their performance as the active site for the reduction of nitrogen to ammonia on TiO$_2$. We find a linear relationship between the d-band center and formation en…
Enhancing Oxygen Reduction Reaction on Pt-Based Electrocatalysts through Surface Decoration for Improved OH Reduction Equilibrium and Reduced H2O Adsorption
