Suppression of Hydrogen Evolution Reaction in Electrochemical N<sub>2</sub> Reduction Using Single-Atom Catalysts: A Computational Guideline

Choi, Changhyeok; Back, Seoin; Kim, Na Young; Lim, Juhyung; Kim, Yong Hyun; Jung, Yousung

doi:10.1021/acscatal.8b00905

Cited by 615 publications

(581 citation statements)

References 50 publications

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“…Therefore, detailed calculation comparing the HER and NRR should be considered for the design of efficiency NRR catalyst. The comparison of H adsorption and N 2 adsorption was previously employed to determine the selectivity between HER and NRR on metal oxide and nitride surface . Here we also did such kind of comparison as shown in Figure 3C‐E.…”

Section: Resultsmentioning

confidence: 99%

Single vs double atom catalyst for N₂ activation in nitrogen reduction reaction: A DFT perspective

Qian

Liu

Zhao

et al. 2020

EcoMat

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Ammonia synthesis through electrochemical reduction of nitrogen molecules is a promising strategy to significantly reduce the energy consumption in traditional industrial process. Detailed mechanism study of multistep complex nitrogen reduction reaction is prerequisite for the design of highly efficient catalyst. Stable atomically dispersed catalyst with unique geometric and electronic structure is suitable for the mechanism clarification of such a complex reaction. In this study, d‐block transition‐metal (TM) anchored C2N single layer catalyst is investigated by the density functional theory (DFT) calculation. Both single TM‐anchored single atom catalyst (SAC) and double TM‐anchored double atom catalyst (DAC) exhibit good thermodynamic stability in atomically dispersed catalyst. In the case of SACs, IVB metals (Ti, Zr, Hf) exhibit the highest reactivity and lowest overpotential. While in the case of DACs, Cr─Cr system leads to the NH3 formation, but V─V system leads to the N2H4 formation. The SACs show much lower overpotential and stronger activation of N2 molecule than the DACs due to the different activation mechanisms: traditional σ‐donation/π‐backdonation N2 activation mechanism is found in SACs, while a new π‐donation/π‐backdonation N2 activation mechanism is found in the DACs. The present work demonstrates that the different catalytic effect for NRR between SAC and DAC and their corresponding electronic structure origin, which gives more insight into the single atom catalyst.

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Section: Resultsmentioning

confidence: 99%

Single vs double atom catalyst for N₂ activation in nitrogen reduction reaction: A DFT perspective

Qian

Liu

Zhao

et al. 2020

EcoMat

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“…Whereas Zr is an extraordinary exception that has the most positive charge (3.00 |e|) among all the screened Mo 2 TiC 2 O 2 ‐TM SA systems. Positively charged reaction center can significantly polarize and then activate the inert N 2 molecule . Hence, these SACs with considerable positively charged dopant, such as Zr and 5 d transition metals, may greatly facilitate the NRR process.…”

Section: Resultsmentioning

confidence: 99%

“…Another issue that limits NRR in acidic condition is the competition with HER. The protons in solution may occupy the active sites and then form H 2 at a comparable limiting potential, reducing the Faradic efficiency of NRR . As mentioned above, electrostatic repulsion can hinder the binding between proton and the positive charged metal, preventing HER process kinetically.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Screening of Single Transition Metal Atoms Embedded in MXene Defects as Superior Electrocatalyst of Nitrogen Reduction Reaction

et al. 2019

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The MXene‐supported single transition metal systems have been reported as promising electrocatalysts for hydrogen evolution reaction (HER) and carbon dioxide reduction reaction. Herein, the potential performance of MXene‐based catalysts was explored on nitrogen reduction reaction (NRR). Density functional theory computations are carried out to screen a series of transition metal atoms confined in a vacancy of MXene nanosheet (Mo2TiC2O2). The results reveal that the Zr, Mo, Hf, Ta, W, Re, and Os supported on defective Mo2TiC2O2 layer can significantly promote the NRR process. Among them, Zr‐doped single atom catalyst (Mo2TiC2O2‐ZrSA) possesses the lowest barrier (0.15 eV) of the potential‐determining step, as well as high selectivity over HER competition. To the best of knowledge, 0.15 eV is the lowest barrier of potential‐determining step that has been reported for NRR so far. Besides, the formation energy of Mo2TiC2O2‐ZrSA is much more negative than that of the synthesized Mo2TiC2O2‐PtSA catalyst, suggesting that the experimental preparation of Mo2TiC2O2‐ZrSA is feasible. This work thus predicts an efficient electrocatalyst for the reduction of N2 to NH3 at ambient conditions.

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“…These binding types exhibit more tunability and are controlled by compositions and crystal structures in comparison to pure metal binding. Through such a tunable binding regulation, not only can the competing HER be suppressed but also an effective electron transfer channel can be established that is conducive for the next activation step.…”

Section: Fundamental Comprehension On Dinitrogen Electroreductionmentioning

confidence: 99%

“…Furthermore, the single atom active components showed intrinsic advantage in suppressing HER. It has been reported that many single atom electrocatalysts have unique electronic structures and lack ensemble effects, both of which hinder H 2 production from hydrogen atoms . For example, Tao et al experimentally showed that single atom Ru anchored at oxygen vacancies suppressed HER ( Figure a) .…”

Section: Design Principles For Electrocatalystsmentioning

confidence: 99%

Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction

et al. 2020

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Ammonia (NH3) is a pivotal precursor in fertilizer production and a potential energy carrier. Currently, ammonia production worldwide relies on the traditional Haber–Bosch process, which consumes massive energy and has a large carbon footprint. Recently, electrochemical dinitrogen reduction to ammonia under ambient conditions has attracted considerable interest owing to its advantages of flexibility and environmental friendliness. However, the biggest challenge in dinitrogen electroreduction, i.e., the low efficiency and selectivity caused by poor specificity of electrocatalysts/electrolytic systems, still needs to be overcome. Although substantial progress has been made in recent years, acquiring most available electrocatalysts still relies on low efficiency trial‐and‐error methods. It is thus imperative to establish some critical guiding principles for nitrogen electroreduction toward a rational design and accelerated development of this field. Herein, a basic understanding of dinitrogen electroreduction processes and the inherent relationships between adsorbates and catalysts from fundamental theory are described, followed by an outline of the crucial principles for designing efficient electrocatalysts/electrocatalytic systems derived from a systematic evaluation of the latest significant achievements. Finally, the future research directions and prospects of this field are given, with a special emphasis on the opportunities available by following the guiding principles.

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Suppression of Hydrogen Evolution Reaction in Electrochemical N₂ Reduction Using Single-Atom Catalysts: A Computational Guideline

Cited by 615 publications

References 50 publications

Single vs double atom catalyst for N₂ activation in nitrogen reduction reaction: A DFT perspective

Single vs double atom catalyst for N₂ activation in nitrogen reduction reaction: A DFT perspective

Theoretical Screening of Single Transition Metal Atoms Embedded in MXene Defects as Superior Electrocatalyst of Nitrogen Reduction Reaction

Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction

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Suppression of Hydrogen Evolution Reaction in Electrochemical N2 Reduction Using Single-Atom Catalysts: A Computational Guideline

Cited by 615 publications

References 50 publications

Single vs double atom catalyst for N2 activation in nitrogen reduction reaction: A DFT perspective

Single vs double atom catalyst for N2 activation in nitrogen reduction reaction: A DFT perspective

Theoretical Screening of Single Transition Metal Atoms Embedded in MXene Defects as Superior Electrocatalyst of Nitrogen Reduction Reaction

Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction

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Suppression of Hydrogen Evolution Reaction in Electrochemical N₂ Reduction Using Single-Atom Catalysts: A Computational Guideline

Single vs double atom catalyst for N₂ activation in nitrogen reduction reaction: A DFT perspective

Single vs double atom catalyst for N₂ activation in nitrogen reduction reaction: A DFT perspective