Generating Defect‐Rich Bismuth for Enhancing the Rate of Nitrogen Electroreduction to Ammonia

Wang, Yue; Shi, Ming; Bao, Di; Meng, Fanlu; Zhang, Qi; Zhou, Yitong; Liu, Kai‐Hua; Zhang, Yan; Wang, Jiazhi; Chen, Zhi‐wen; Liu, Dapeng; Jiang, Zheng; Luo, Ming; Gu, Lin; Zhang, Qinghua; Cao, Xingzhong; Yao, Yao; Shao, Minhua; Zhang, Yu; Zhang, Xinbo; Chen, Jingguang G.; Yan, Jun‐Min; Jiang, Qing

doi:10.1002/anie.201903969

Cited by 237 publications

(142 citation statements)

References 29 publications

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“…Based on the above‐mentioned thorough analysis and characterization, the NRR performance of IrP 2 @PNPC‐NF was measured to evaluate its electrocatalytic N 2 reduction ability using a typical two‐compartment cell separated by a proton exchange membrane. Before the NRR tests, the safety of the test environment was first performed by the blank experiments, including the fresh 0.05 m H 2 SO 4 solution and the stale 0.05 m H 2 SO 4 electrolyte treated by N 2 gas bubbling for 1 h. [ 36 ] As shown in Figure S7 in the Supporting Information, no absorption peaks are detected at a wavelength of 655 nm, indicating that there are no possible adventitious contaminations from the water medium and the high purity feeding N 2 gas, respectively. [ 37,38 ] To preliminarily probe the NRR activity of IrP 2 @PNPC‐NF, the linear sweep voltammetry (LSV) was performed in Ar‐ and N 2 ‐saturated 0.05 m H 2 SO 4 solution.…”

Section: Resultsmentioning

confidence: 99%

“…Here, we quote the concept of the roughness factors (RFs) reported by previous papers, where the inherent activity can be obtained by normalizing the ECSA surface area. [ 36,39–41 ] Supposing that IrP 2 @PNC‐NP has the RF value of 1, the RF of IrP 2 @PNPC‐NF can be calculated in the light of C dl processed by cyclic voltammetry (CV) data (see the Experimental Section in detail). As shown in Figure 3f, the normalized NH 3 yield of IrP 2 @PNPC‐NF (46.3 µg h −1 mg −1 ) still has an about threefold improvement compared with that of its counterpart, indicating an increase of the intrinsic activity.…”

Section: Resultsmentioning

confidence: 99%

“…As shown in Figure S18 in the Supporting Information, the C dl value is the slope of the linear regression, which is fitted by plotting the current density variation (Δ j = ( j a − j c )/2, at 0 V vs Ag/AgCl) against scan rate. Based on the previous reports, [ 36,41,49 ] RF of IrP 2 @PNPC‐NF was further calculated by dividing its capacitance by that of IrP 2 @PNC‐NP (supposing an RF value of 1 for IrP 2 @PNC‐NP).…”

Section: Methodsmentioning

confidence: 99%

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Low‐Coordinate Step Atoms via Plasma‐Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Yang

Ling

et al. 2020

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history because of its important role in facilitating the production of food and maintaining the growth of the human population. [1,2] Benefiting from its high energy density, zero-carbon emissions, and facile storage and transportation, ammonia (NH 3 ) is also being considered as a high-efficiency hydrogen fuel carrier. [3][4][5] Relative to the traditional energy-and capital-intensive HBP, the electrochemical N 2 reduction reaction (NRR) powered by renewable electricity occurs under ambient conditions using the H 2 O and N 2 as feedstock materials and is an environment-friendly process for distributed, modular synthesis of NH 3 . [6][7][8][9] Therefore, electrochemical reduction of N 2 to NH 3 has been considered as a potentially promising alternative to HBP and has recently received great interest. [10][11][12] The challenge for the development of the electrochemical NRR in practice is that N 2 molecule has low polarizability and is highly stable and inert (with strong bond energy of 940.95 kJ mol −1 ), which makes it difficult to cleaved and reduce to NH 3 by hydrogenation. [13,14] To this end, numerous efforts, both theoretical and experimental, have been devoted to the exploration of high-efficiency NRR electrocatalysts. In response, the suggested noble metals, such as Ir, Pt, Ru, and Rh, possess relatively optimized nitrogen binding for The electrochemical N 2 reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber-Bosch process for distributed and modular production of NH 3 . Nevertheless, developing high-efficiency catalysts to simultaneously realize both high activity and selectivity for the development of a sustainable NRR is very critical but extremely challenging. Here, a unique plasma-assisted strategy is developed to synthesize iridium diphosphide nanocrystals with abundant surface step atoms anchored in P,N-codoped porous carbon nanofilms (IrP 2 @PNPC-NF), where the edges of the IrP 2 nanocrystals are extremely irregular, and the ultrathin PNPC-NF possesses a honeycomb-like macroporous structure. These characteristics ensure that IrP 2 @PNPC-NF delivers superior NRR performance with an NH 3 yield rate of 94.0 µg h −1 mg −1 cat. and a faradaic efficiency (FE) of 17.8%. Density functional theory calculations reveal that the unique NRR performance originates from the low-coordinate step atoms on the edges of IrP 2 nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH 3 formation. More importantly, such a plasma-assisted strategy is general and can be extended to the synthesis of other high-melting-point noble-metal phosphides (OsP 2 @PNPC-NF, Re 3 P 4 @PNPC-NF, etc.) with abundant step atoms at lower temperatures. Scheme 1. Schematic illustration of the synthesis of honeycomb-like macroporous IrP 2 @PNPC-NF with abundant step atoms by a new strategy of plasma-assisted calcination and its application for the electrochemical reduction of N 2 to NH 3 . 3 of 10) www.advanceds...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Low‐Coordinate Step Atoms via Plasma‐Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Yang

Ling

et al. 2020

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“…With this regard, pioneering work has been conducted to overcome this difficulty, such as widening the potential gap between NRR and the hydrogen evolution reaction (HER) and designing active centers with intrinsic preference for nitrogen adsorption . Although either a superior Faradic Efficiency (FE) or an outstanding ammonia production rate has been achieved on these catalysts, to simultaneously achieve these two merits is still challenging.…”

Section: Figurementioning

confidence: 99%

Vacancy Engineering of Iron‐Doped W₁₈O₄₉ Nanoreactors for Low‐Barrier Electrochemical Nitrogen Reduction

et al. 2020

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The electrochemical nitrogen reduction reaction (NRR) is a promising energy-efficient and low-emission alternative to the traditional Haber-Bosch process. Usually, the competing hydrogen evolution reaction (HER) and the reaction barrier of ambient electrochemical NRR are significant challenges, making a simultaneous high NH 3 formation rate and high Faradic efficiency (FE) difficult. To give effective NRR electrocatalysis and suppressed HER, the surface atomic structure of W 18 O 49 , which has exposed active W sites and weak binding for H 2 , is doped with Fe. A high NH 3 formation rate of 24.7 mg h À1 mg cat À1 and a high FE of 20.0 % are achieved at an overpotential of only À0.15 V versus the reversible hydrogen electrode. Ab initio calculations reveal an intercalation-type doping of Fe atoms in the tunnels of the W 18 O 49 crystal structure, which increases the oxygen vacancies and exposes more W active sites, optimizes the nitrogen adsorption energy, and facilitates the electrocatalytic NRR.

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“…[5][6][7][8] Noble metals perform the NRR efficiently;however, their scarcity and high cost limits their application in large-scale N 2 reduction. [12][13][14][15][16][17][18][19][20][21][22][23][24] TiO 2 is highly adaptable as asemiconductor catalyst because of its long-term thermodynamic stability,n atural abundance,a nd nontoxicity. [12][13][14][15][16][17][18][19][20][21][22][23][24] TiO 2 is highly adaptable as asemiconductor catalyst because of its long-term thermodynamic stability,n atural abundance,a nd nontoxicity.…”

mentioning

confidence: 99%

Greatly Improving Electrochemical N₂ Reduction over TiO₂ Nanoparticles by Iron Doping

Zhu

Xing

et al. 2019

Angewandte Chemie

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Titanium-based catalysts are needed to achieve electrocatalytic N 2 reduction to NH 3 with alarge NH 3 yield and ahigh Faradaic efficiency (FE). One of the cheapest and most abundant metals on earth, iron, is an effective dopant for greatly improving the nitrogen reduction reaction (NRR) performance of TiO 2 nanoparticles in ambient N 2 -to-NH 3 conversion. In 0.5 m LiClO 4 ,F e-doped TiO 2 catalyst attains ah igh FE of 25.6 %a nd al arge NH 3 yield of 25.47 mgh À1 mg cat À1 at À0.40 Vv ersus ar eversible hydrogen electrode.This performance compares favorably to those of all previously reported titanium-and iron-based NRR electrocatalysts in aqueous media. The catalytic mechanism is further probed with theoretical calculations.Asanessential activated nitrogen source,NH 3 is extensively used to manufacture dyes,p olymers,f ertilizers,a nd explosives,and it also serves as carbon-neutral energy carrier with high energy density. [1][2][3] To date,the dominant industrial route for NH 3 synthesis is the Haber-Bosch process using N 2 and H 2 as the feeding gases,b ut this process operates at high temperature and high pressure,a nd consumes al arge amount of energy while emitting CO 2 . [4] Electrochemical N 2 reduction offers an attractive alternative in an environmentally benign and sustainable manner,b ut the strong N N bond is fairly inert and thus difficult to break in ac hemical reaction, underlying the need for electrocatalysts with high activity in the nitrogen reduction reaction (NRR). [5][6][7][8] Noble metals perform the NRR efficiently;however, their scarcity and high cost limits their application in large-scale N 2 reduction. [8][9][10][11] NRR research has thus shifted to development of noble-metal-free alternatives. [12][13][14][15][16][17][18][19][20][21][22][23][24] TiO 2 is highly adaptable as asemiconductor catalyst because of its long-term thermodynamic stability,n atural abundance,a nd nontoxicity. [25] Recent studies have demonstrated that TiO 2 with oxygen defects has good electrocatalytic activity for the NRR, [26,27] and heteroatoms (B, [28] C, [29] V, [30] and Zr, [31] )a re effective dopants to enhance the NRR performances of TiO 2 catalysts. However,T i-based catalysts that simultaneously achieve al arge NH 3 yield with ah igh Faradaic efficiency (FE) are not available thus far.As one of the cheapest and most abundant metals on the earth, [32] Fe also exists in biological nitrogenases for natural N 2 fixation. [33] Fe compounds have been widely utilized as catalysts for artificial N 2 fixation in the Haber-Bosch [4] and electrochemical [34][35][36][37][38][39] processes.I ti st hus natural for us to explore use of Fe as ad opant for TiO 2 ,w hich has not been reported before.Herein, we report on our recent experimental results that Fe-doped TiO 2 is superior in performances for electrocatalytic N 2 reduction under ambient conditions.I n 0.5 m LiClO 4 ,t his catalyst achieves ah igh FE of 25.6 %a nd al arge NH 3 yield of 25.47 mgh À1 mg cat À1 at À0.40 Vv ersus ar eversible hydrogen electrode (...

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Generating Defect‐Rich Bismuth for Enhancing the Rate of Nitrogen Electroreduction to Ammonia

Cited by 237 publications

References 29 publications

Low‐Coordinate Step Atoms via Plasma‐Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Low‐Coordinate Step Atoms via Plasma‐Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Vacancy Engineering of Iron‐Doped W₁₈O₄₉ Nanoreactors for Low‐Barrier Electrochemical Nitrogen Reduction

Greatly Improving Electrochemical N₂ Reduction over TiO₂ Nanoparticles by Iron Doping

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Generating Defect‐Rich Bismuth for Enhancing the Rate of Nitrogen Electroreduction to Ammonia

Cited by 237 publications

References 29 publications

Low‐Coordinate Step Atoms via Plasma‐Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Low‐Coordinate Step Atoms via Plasma‐Assisted Calcinations to Enhance Electrochemical Reduction of Nitrogen to Ammonia

Vacancy Engineering of Iron‐Doped W18O49 Nanoreactors for Low‐Barrier Electrochemical Nitrogen Reduction

Greatly Improving Electrochemical N2 Reduction over TiO2 Nanoparticles by Iron Doping

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Vacancy Engineering of Iron‐Doped W₁₈O₄₉ Nanoreactors for Low‐Barrier Electrochemical Nitrogen Reduction

Greatly Improving Electrochemical N₂ Reduction over TiO₂ Nanoparticles by Iron Doping