Metal-free black phosphorus nanosheets-decorated graphitic carbon nitride nanosheets with C P bonds for excellent photocatalytic nitrogen fixation

Qiu, Pengxiang; Xu, Chenmin; Zhou, Ning; Chen, Huan; Jiang, Fang

doi:10.1016/j.apcatb.2017.09.010

Cited by 260 publications

(124 citation statements)

References 37 publications

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“…As we know, the g‐C 3 N 4 ‐based photocatalysts and electrocatalysts have recently demonstrated high catalytic activity toward the NRR to NH 3 at ambient conditions 7,9,34. However, owing to abundant N atoms contained in g‐C 3 N 4 , a still concerned issue associated with the NRR is if the exposed active N (e.g., edge or amino N) atoms in g‐C 3 N 4 catalysts would be hydrogenated and participant in the formation of NH 3 .…”

Section: Resultsmentioning

confidence: 99%

Formation of BNC Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C₃N₄ for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance

Wang

Zhou

Liu

et al. 2020

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It is an important issue that exposed active nitrogen atoms (e.g., edge or amino N atoms) in graphitic carbon nitride (g‐C3N4) could participate in ammonia (NH3) synthesis during the photocatalytic nitrogen reduction reaction (NRR). Herein, the experimental results in this work demonstrate that the exposed active N atoms in g‐C3N4 nanosheets can indeed be hydrogenated and contribute to NH3 synthesis during the visible‐light photocatalytic NRR. However, these exposed N atoms can be firmly stabilized through forming BNC coordination by means of B‐doping in g‐C3N4 nanosheets (BCN) with a B‐doping content of 13.8 wt%. Moreover, the formed BNC coordination in g‐C3N4 not only effectively enhances the visible‐light harvesting and suppresses the recombination of photogenerated carriers in g‐C3N4, but also acts as the catalytic active site for N2 adsorption, activation, and hydrogenation. Consequently, the as‐synthesized BCN exhibits high visible‐light‐driven photocatalytic NRR activity, affording an NH3 yield rate of 313.9 µmol g−1 h−1, nearly 10 times of that for pristine g‐C3N4. This work would be helpful for designing and developing high‐efficiency metal‐free NRR catalysts for visible‐light‐driven photocatalytic NH3 synthesis.

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Section: Resultsmentioning

confidence: 99%

Formation of BNC Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C₃N₄ for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance

Wang

Zhou

Liu

et al. 2020

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“…Till now, many semiconductor photocatalysts such as Ga 2 O 3 , g‐C 3 N 4 , and TiO 2 have been employed for nitrogen fixation under visible light irradiation, and obtain the superior photocatalytic nitrogen fixation efficiency. Recently, Chen and co‐workers reported a high efficient metal‐free BP/g‐C 3 N 4 heterojunction photocatalyst with CP bonds for catalytic nitrogen fixation . The catalytic nitrogen fixation measurement under visible light illumination showed that BP/g‐C 3 N 4 nanocomposite displayed excellent photocatalytic performance, and the highest catalytic production can be achieved to 347.5 µmol L −1 h −1 by 0.05 BP/g‐C 3 N 4 , which was much larger than pure g‐C 3 N 4 nanosheets (40.5 µmol L −1 h −1 ) and even higher than 0.05 Pt/g‐C 3 N 4 ( Figure ).…”

Section: Photocatalysis Applicationsmentioning

confidence: 99%

Black Phosphorus, a Rising Star 2D Nanomaterial in the Post‐Graphene Era: Synthesis, Properties, Modifications, and Photocatalysis Applications

Lai

Zeng

et al. 2019

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Semiconductor photocatalysis, a sustainable and renewable technology, is deemed to be a new path to resolve environmental pollution and energy shortage. The development of effective photocatalysts, especially the metal‐free photocatalysts, is a critical determinant of this technique. The recently emerged 2D material of black phosphorus with distinctive properties of tunable direct bandgap, ultrahigh charge mobility, fortified optical absorption, large specific surface area, and anisotropic structure has captured enormous attention since the first exfoliation of bulk black phosphorus into mono‐ or few layered phosphorene in 2014. In this article, the state‐of‐the‐art preparation methods are first summarized for bulk black phosphorus, phosphorene, and black phosphorus quantum dot and then the fundamental structure and electronic and optical properties are analyzed to evaluate its feasibility as a metal‐free photocatalyst. Various modifications on black phosphorus are also summarized to enhance its photocatalytic performance. Furthermore, the multifarious applications such as solar to energy conversion, organic removal, disinfection, nitrogen fixation, and photodynamic therapy are discussed and some of the future challenges and opportunities for black phosphorus research are proposed. This review reveals that the rising star of black phosphorus will be a multifunctional material in the postgraphene era.

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“…[25,26] Some recent studies have shown that the use of nonmetallic components as active centers may be an effective way to obtain high selectivity. [35][36][37][38][39][40] Notably,s uch inherent features should facilitate chemisorp-Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi. [29] Similar nitrogen reduction activity was also observed on metal-free boron carbide nanosheets.…”

mentioning

confidence: 99%

“…[32] In particular,b lack phosphorus is atype of layered crystal (Figure 1a,b;Supporting Information, Figure S1) with monolayers stacked together via weak, interlayer van der Waals interactions; [33,34] these interactions allow black phosphorus to be exfoliated into monolayer phosphorene or few-layer black phosphorus, releasing the maximum number of intrinsic active sites. [35][36][37][38][39][40] Notably,s uch inherent features should facilitate chemisorp-tion of N 2 molecules and provide sufficient electrons for activation of the inert N Ntriple bond. As aproof of concept, few-layer black phosphorus nanosheets have af aradaic efficiency and NH 3 production rate for the NRR in an acidic aqueous solution (0.01m HCl) as high as 5.07 %a nd 31.37 mgh À1 mg À1 cat.…”

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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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Metal-free black phosphorus nanosheets-decorated graphitic carbon nitride nanosheets with C P bonds for excellent photocatalytic nitrogen fixation

Cited by 260 publications

References 37 publications

Formation of BNC Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C₃N₄ for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance

Formation of BNC Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C₃N₄ for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance

Black Phosphorus, a Rising Star 2D Nanomaterial in the Post‐Graphene Era: Synthesis, Properties, Modifications, and Photocatalysis Applications

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

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Metal-free black phosphorus nanosheets-decorated graphitic carbon nitride nanosheets with C P bonds for excellent photocatalytic nitrogen fixation

Cited by 260 publications

References 37 publications

Formation of BNC Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C3N4 for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance

Formation of BNC Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C3N4 for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance

Black Phosphorus, a Rising Star 2D Nanomaterial in the Post‐Graphene Era: Synthesis, Properties, Modifications, and Photocatalysis Applications

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

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Formation of BNC Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C₃N₄ for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance

Formation of BNC Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C₃N₄ for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance