Single transition metal atom anchored on g-C3N4 as an electrocatalyst for nitrogen fixation: A computational study

Zhang, Nan; Gao, Yaping; Ma, Lixia; Wang, Yuyang; Huang, Luo; Wei, Baoqiang; Xue, Yi; Zhu, Houyu; Jiang, Ruibin

doi:10.1016/j.ijhydene.2022.09.074

Cited by 19 publications

(7 citation statements)

References 51 publications

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“…The catalysts would be screened based on the catalytic performance of three typical NRR pathways, namely, the alternating, distal, and enzymatic mechanisms. , Among them, alternating and distal mechanisms start with end-on adsorption as the initial N 2 adsorption configuration, that is, only one N atom is bonded to the surface of the catalyst, while the enzymatic mechanism starts with side-on adsorption, and both N atoms interact with the catalyst (Figure ). The intermediates of all three reaction mechanisms on six catalysts were optimized, and the relative free-energy changes at each step were calculated and are shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…Considering the aforementioned reasons, we investigated six TMs, V, Mn, Fe, Co, Ni, and Cu, as shown in Figure a. Previous studies ,, have shown that the hollow sites of the triangle composed of the N atoms on three triazines are the optimal location for anchoring TM atoms (Figure b), compared to other potential sites. The optimized structures of TM atoms binding to g-C 3 N 4 suggest coordination numbers of 3 or 5.…”

Section: Resultsmentioning

confidence: 99%

“…Accordingly, we started the investigation from five consecutive TMs, ranging from manganese (Mn) to copper (Cu), as potential dopants on g-C 3 N 4 . Furthermore, we expanded our research scope based on recent findings by Zhang et al, 38 which highlighted the advantageous NRR catalytic activity of vanadium(V)@g-C 3 N 4 ; we extended the search scope to include V. The energy step diagrams of NRR were computed for each catalyst across three distinct NRR mechanisms. The identification of the optimal catalyst for each reaction mechanism was accomplished by the initial potential.…”

Section: Introductionmentioning

confidence: 99%

“…(2) It has high light adsorption performance and activation ability for N 2. , Single-atom catalyst (SAC) has high atomic utilization rate and excellent catalytic performance; in addition, the strong interaction between the separated metal atoms and the supports helps to achieve good stability of SAC. − Graphitic carbon nitride (g-C 3 N 4 ) has been proven by numerous studies to be a good support for single-atom multiphase catalysts; the presence of nitrogen-rich gaps between triazine units gives the support unique potential to stabilize various metal species, such as single metal atoms. − For example, Wang et al reported a metal-free single-atom photocatalyst B@g-C 3 N 4 for NRR for the first time. First-principles calculations showed that gas-phase N 2 can be effectively reduced to NH 3 through an enzymatic mechanism on B@g-C 3 N 4 .…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A First-Principles and Machine Learning Study on Design of Graphitic Carbon Nitride-Based Single-Atom Photocatalysts

Chen,

Yang,

Chen

2024

ACS Appl. Nano Mater.

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Photocatalytic nitrogen fixation offers an efficient, environmentally friendly, and energy-saving approach for ammonia synthesis. In this study, semiconductor materials, particularly graphitic carbon nitride (g-C 3 N 4 ) combined with single metal atoms, were theoretically investigated to identify promising candidates as nitrogen fixation photocatalysts. Initially, six different single 3d transition-metal atoms, i.e., V, Mn, Fe, Co, Ni, and Cu, were loaded onto g-C 3 N 4 , and the optimal single-atom catalyst, Fe@g-C 3 N 4 , was selected through reaction energy calculations. This catalyst demonstrated excellent performance in terms of the electronic structure and light absorption properties. Furthermore, machine learning methods were applied to a limited sample set to predict a catalyst with a superior performance beyond the computational samples. Utilizing a backward elimination method and sure independence screening and sparsifying operator (SISSO) training, the key descriptors correlated with the target properties of the catalysts were identified. The SISSO descriptors, consisting of structural and electronic characteristic parameters, are interpretable and provide meaningful insights. Importantly, a catalyst, Ru@g-C 3 N 4 , with outstanding performance was predicted and verified by density functional theory calculations. This catalyst design strategy demonstrates promising results with limited computational data, highlighting the potential of combining theoretical simulations with machine learning methods for catalyst design.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A First-Principles and Machine Learning Study on Design of Graphitic Carbon Nitride-Based Single-Atom Photocatalysts

Chen,

Yang,

Chen

2024

ACS Appl. Nano Mater.

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“…Within the group of 2D substrates, graphitic carbon-nitride (g-C 3 N 4 ) has been identified as a promising substrate for anchoring single atoms due to its unique six-fold cavities, low cost, and accessibility, making it a good candidate for realizing TM-SACs [22,23]. It has been recently reported that TM-doped g-C 3 N 4 catalysts are potential candidates for various applications such as nitrogen electroreduction [24], nitrogen fixation [25,26], efficient photocatalysts, and electrocatalysts [23,27,28].…”

Section: Introductionmentioning

confidence: 99%

Computational design of single-atom catalysts embedded on reduced graphitic carbon nitride monolayers

Jakhar,

Ding,

Fahlman

et al. 2024

Nano Ex.

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The design of efficient single-atom catalysts (SACs) with optimal activity and selectivity for sustainable energy and environmental applications remains a challenge. In this work, comprehensive first-principles calculations are performed to validate the feasibility of single TM atoms (3d, 4d, and 5d series) embedded in two different conformations of graphitic carbon nitride (g-C3N4) monolayers. Additionally, we investigate the effect of nitrogen vacancies in the g-C3N4 monolayers on the absorption of SACs considering three potential absorption scenarios that correspond to different experimental conditions. Our results point to the most stable configurations with the lowest formation energies and indicate that the absorption of single TM atoms on-vacancy and on-center sites are more favorable than via-substitution. In addition to the thermodynamic stability, electrochemical stability is also investigated through the calculation of the dissolution potential of the SACs. Within the scenarios considered in this study, we find that Pt, Pd, Rh, Au, Ru, Ir, Cu, Co, Fe, and Ni will produce the most robust SACs on both (edge and bridge) N vacancy site of reduced g-C3N4. Our findings provide guidance for the design and development of g-C3N4 sheets decorated with single TM atoms for technological applications such as pollutant degradation, CO2 reduction, N2 fixation, selective oxidation, water splitting, and metal ion-based batteries.

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Graphitic Carbon Nitride Supported Boron Quantum Dots: A Transition Metal Free Alternative for Di‐Nitrogen to Ammonia Reaction

Samudre,

Krishnamurty

2024

ChemPhysChem

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Presently, a sustainable electrochemical Nitrogen Reduction Reaction (NRR) has been essentially found to be viable on transition metal‐based catalysts. However, metal free catalysts, being cost effective and non‐corrosive, present an ideal solution for a sustainable world. Herein, through a DFT based study, we demonstrate a metal free NRR catalysts, boron quantum dots with 13 atoms as a case study, and their chemically modified counterparts when anchored on graphitic carbon nitride (g‐C3N4) surface. The best catalyst among the studied, a silicon doped boron quantum dot with a cagelike structure, is found to favour the dinitrogen to ammonia reaction path way with a low liming potential and potential rate‐determining step (PDS) of ‐0.11 V and 0.27 eV, respectively. The present work demonstrates as to how boron quantum dots, which are reported to be experimentally synthesised, can be exploited for ammonia synthesis when supported on surface. These catalysts effectively suppress the HER, thus establishing its suitability as an ideal catalyst. The work also represents a futuristic pathway towards a metal free catalyst for NRR.

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Single transition metal atom anchored on g-C3N4 as an electrocatalyst for nitrogen fixation: A computational study

Cited by 19 publications

References 51 publications

A First-Principles and Machine Learning Study on Design of Graphitic Carbon Nitride-Based Single-Atom Photocatalysts

A First-Principles and Machine Learning Study on Design of Graphitic Carbon Nitride-Based Single-Atom Photocatalysts

Computational design of single-atom catalysts embedded on reduced graphitic carbon nitride monolayers

Graphitic Carbon Nitride Supported Boron Quantum Dots: A Transition Metal Free Alternative for Di‐Nitrogen to Ammonia Reaction

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