The incorporation of oxygen vacancy defects into the catalysts has been attracting significant interest for regulating the performance of photocatalysts. Single-atomic-site metal catalysts have als...

Interaction of Single-Atom Platinum–Oxygen Vacancy Defects for the Boosted Photosplitting Water H2 Evolution and CO2 Photoreduction: Experimental and Theoretical Study

Regulation of oxygen vacancies in SrTiO3 perovskite for efficient photocatalytic nitrogen fixation

Photothermal Catalysis for Selective CO2 Reduction on the Modified Anatase TiO2 (101) Surface

Large-scale ammonia synthesis via the electrochemical nitrogen reduction reaction (eNRR) under mild reaction conditions represents a green prospect for agriculture, industry, and energy. This bioinspired and carbon-free reaction has been proposed as an ideal alternative to the Haber–Bosch process. However, the yield and selectivity of the current eNRR have not met the requirements for industrialization. Mechanistic understanding and catalysts’ design are still long-term pursuits in this field, where theoretical simulations will have significant contributions. In this Review, we will start with the natural N2 fixation enzymes, the nitrogenases, followed by a summary of the key experimental eNRR performances on hundreds of recently reported catalysts, and we analyze the general trend and challenges before eNRR can significantly impact the ammonia industry. Then, we will systematically review the recent progress and contributions of computational studies in understanding the reaction mechanism and rational catalyst design for eNRR. The fundamental principles, reaction mechanisms, crucial theoretical criteria, modeling methods, and computationally predicted catalysts for eNRR are systematically summarized and discussed. Finally, we outline the current challenges and future opportunities for experimental and computational studies of electrochemical N2 reduction. 

Progress of Experimental and Computational Catalyst Design for Electrochemical Nitrogen Fixation

Environmentally benign CeO2-WO3/TiO2 catalysts are promising alternatives to commercial toxic V2O5-WO3/TiO2 for controlling NOx emission via selective catalytic reduction (SCR), but the insufficient catalytic activity of CeO2-WO3/TiO2 catalysts is one of the obstacles in their applications because of a lack of an in-depth understanding of the CeO2-WO3 interactions. Herein, we design a Ce1-W1/TiO2 model catalyst by anchoring Ce1-W1 atom pairs on anatase TiO2(001) to investigate the synergy between Ce and W in SCR. A series of characterizations combined with density functional theory calculations and in situ diffuse-reflectance infrared Fourier-transform experiments reveal that there exists a strong electronic interaction within Ce1-W1 atom pairs, leading to a much better SCR performance of Ce1-W1/TiO2 compared with that of Ce1/TiO2 and W1/TiO2. The Ce1-W1 synergy not only shifts down the lowest unoccupied states of Ce1 near the Fermi level, thus enhancing the abilities in adsorbing and oxidizing NH3 but also makes the frontier orbital electrons of W1 delocalized, thus accelerating the activation of O2. The deep insight of the Ce-W synergy may assist in the design and development of efficient catalysts with an SCR activity as high as or even higher than V2O5-WO3/TiO2.

Abatement of Nitrogen Oxides via Selective Catalytic Reduction over Ce1-W1 Atom-Pair Sites.

Exploration of TiO2 as substrates for single metal catalysts: A DFT study

First principles study of single Fe atom supported on TiO2(0 0 1) for nitrogen reduction to ammonia

Mechanistic Insights into Direct Methane Oxidation to Methanol on Single-Atom Transition-Metal-Modified Graphyne

Catalytic reduction of carbon dioxide over two-dimensional boron monolayer

Instead of the energy-intensive Haber-Bosch process, electrochemical nitrogen reduction reaction (NRR) is an exciting new carbon neutral technique for ammonia synthesis under ambient conditions. In this work, we investigated K-based electrocatalysts theoretically and demonstrated that K3Sb/graphene performs excellent activity and inhibits hydrogen evolution on alternating reaction pathway. The first hydrogenation step from N2* to NNH* was found to be the most energetic and limiting step (0.61 eV). Graphene substrate plays the critical role to promote electronic conductivity between K3Sb and dinitrogen.

Tianyi Wang

Papers

Exploration of TiO2 as substrates for single metal catalysts: A DFT study

First principles study of single Fe atom supported on TiO2(0 0 1) for nitrogen reduction to ammonia

Mechanistic Insights into Direct Methane Oxidation to Methanol on Single-Atom Transition-Metal-Modified Graphyne

Catalytic reduction of carbon dioxide over two-dimensional boron monolayer

Theoretical study of K3Sb/graphene heterostructure for electrochemical nitrogen reduction reaction