Defect Engineering Metal‐Free Polymeric Carbon Nitride Electrocatalyst for Effective Nitrogen Fixation under Ambient Conditions

Lv, Chade; Qian, Yumin; Yan, Chunshuang; Ding, Yu; Liu, Yuanyue; Chen, Gang; Yu, Guihua

doi:10.1002/anie.201806386

Cited by 669 publications

(412 citation statements)

References 42 publications

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“…Due to the wide application in agriculture and chemical industry, ammonia has enormous global demand . Most synthetic ammonia is produced by the Haber–Bosch process that is conducted at harsh conditions (400–500 °C and 150–250 atm) and consumes a large amount of energy . Inspired by the biological nitrogen fixation, the electrochemical nitrogen reduction reaction (NRR) is considered to be an economic and environmentally friendly alternative for the Haber–Bosch process.…”

Section: Introductionmentioning

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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Section: Introductionmentioning

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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“…[12][13][14][15] To this end, the search for an electrocatalytic NRR center in recent years has mainly focused on transition-metal-based materials. [27][28][29][30][31] Fore xample, Yu et al reported ah igh NH 3 production rate and faradaic efficiency by using boron-doped graphene as am etal-free NRR catalyst under ambient conditions. [7] It is worthwhile to note that although an unoccupied nonbonding orbital and electron donor site with abundant electron cloud density are prerequisites for aN RR catalyst, the do rbital electrons in transition metals also benefit the formation of metal-hydrogen bonds,w hich will exacerbate the competitive hydrogen evolution reaction and limit the nitrogen reduction selectivity and catalytic efficiency.…”

mentioning

confidence: 99%

“…[24] Compared to transition metals,t he weak hydrogen adsorption of nonmetallic elements and their abundant valence electrons should provide am ore ideal nitrogen activation center. [27][28][29][30][31] Fore xample, Yu et al reported ah igh NH 3 production rate and faradaic efficiency by using boron-doped graphene as am etal-free NRR catalyst under ambient conditions. [27][28][29][30][31] Fore xample, Yu et al reported ah igh NH 3 production rate and faradaic efficiency by using boron-doped graphene as am etal-free NRR catalyst under ambient conditions.…”

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confidence: 99%

Ammonia Synthesis Under Ambient Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets

et al. 2019

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Constructing efficient catalysts for the N 2 reduction reaction (NRR) is am ajor challenge for artificial nitrogen fixation under ambient conditions.H erein, inspired by the principle of "like dissolves like", it is demonstrated that am ember of the nitrogen family,w ell-exfoliated few-layer black phosphorus nanosheets (FL-BP NSs), can be used as an efficient nonmetallic catalyst for electrochemical nitrogen reduction. The catalyst can achieve ah igh ammonia yield of 31.37 mgh À1 mg À1cat. under ambient conditions.D ensity functional theory calculations reveal that the active orbital and electrons of zigzag and diff-zigzag type edges of FL-BP NSs enable selective electrocatalysis of N 2 to NH 3 via an alternating hydrogenation pathway.T his work proves the feasibility of using an onmetallic simple substance as an itrogen-fixing catalyst and thus opening an ew avenue towardst he development of more efficient metal-free catalysts. Ammonia (NH 3 )i sabasic raw chemical material used in modern industry and agriculture. [1] At present, the energyintensive Haber-Bosch process is the main artificial synthesis route for ammonia, and this process uses more than 1% of global annual energy consumption and produces carbon dioxide emissions. [2,3] In contrast, electrochemical reduction of nitrogen into ammonia under ambient conditions is ap otential strategy for sustainable ammonia production. [4][5][6] However,o wing to the strong dipole moment of the N N triple bond and the vigorous competing hydrogen evolution reaction (HER), [7][8][9][10][11] the development of highly effective catalysts with sufficient activity and selectivity is essential.According to available experimental and theoretical NRR data, an active center that can easily adsorb nitrogen molecules and sufficiently activate the N Nt riple bond is very desirable. [12][13][14][15] To this end, the search for an electrocatalytic NRR center in recent years has mainly focused on transition-metal-based materials. [8,[14][15][16][17][18][19][20][21][22][23] Specifically,b enefiting from the unoccupied and occupied dorbitals of transition metals,t he electron density from N 2 is synergically accepted with appropriate energy and symmetry,a nd then, the transition metal donates electrons to the p*o rbital of NN, strengthening N 2 adsorption and weakening the NNbond. [7] It is worthwhile to note that although an unoccupied nonbonding orbital and electron donor site with abundant electron cloud density are prerequisites for aN RR catalyst, the do rbital electrons in transition metals also benefit the formation of metal-hydrogen bonds,w hich will exacerbate the competitive hydrogen evolution reaction and limit the nitrogen reduction selectivity and catalytic efficiency. [24] Compared to transition metals,t he weak hydrogen adsorption of nonmetallic elements and their abundant valence electrons should provide am ore ideal nitrogen activation center. [25,26] Some recent studies have shown that the use of nonmetallic components as active centers may be an effective way to obta...

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Section: Design Principles For Electrocatalystsmentioning

confidence: 99%

“…In particular, N vacancies were deliberately engineered in polymeric carbon nitride. A significantly enhanced activity was obtained via end‐on binding of dinitrogen in these vacancies, which increased the bond length and promoted spatial electron transfer . It is strongly recommended that isotopic labeling experiment using 15 N 2 feed gas should be done to determine the mechanism of NRR in N‐containing electrocatalysts.…”

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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Defect Engineering Metal‐Free Polymeric Carbon Nitride Electrocatalyst for Effective Nitrogen Fixation under Ambient Conditions

Cited by 669 publications

References 42 publications

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

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

Ammonia Synthesis Under Ambient Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets

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

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