ZIF‐Induced d‐Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

Chen, Jaslyn Ru Ting; Koh, Charlynn Sher Lin; Lee, Hiang Kwee; Han, Xuemei; Phan‐Quang, Gia Chuong; Pang, Jing; Lay, Chee Leng; Pedireddy, Srikanth; Phang, In Yee; Yeow, Edwin K. L.; Ling, Xing Yi

doi:10.1002/ange.202006071

Cited by 32 publications

(10 citation statements)

References 34 publications

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“…A lowering in the d-band center of the surface-active site is known to weaken the H-adsorption. 35,59 DFT simulations for this work reflect that, when SnS 2 was interfaced with NPG, the d-band center of the surface Sn atom, active for the NRR, shifted from −2.91 eV for pristine SnS 2 to −3.47 eV for NPG@SnS 2 (Figure 6a). This deviation reflected that the HER would be suppressed at the active site, resulting in the facile adsorption of N 2 initiating the NRR.…”

Section: Resultsmentioning

confidence: 66%

“…34 This interfacial effect also modulates the d-band center of the surfaceactive atoms that widely help to suppress the competitive HER. 35 The accessibility of free charge carriers is reflected in the conductivity of the semiconductor that reinforces the kinetics of the proton-coupled electron transfer process (NRR) that requires six electrons and six protons to completely get reduced to ammonia, whereas the HER involves much faster kinetics with only two electrons and two protons. 36 Furthermore, the dissociation of the NN requires a high energy barrier and thus is thermodynamically not favorable.…”

Section: Introductionmentioning

confidence: 96%

“…A Mott–Schottky effect operating at the interface induces a lowered work function of the heterostructure with an elevated flat band Fermi level . This interfacial effect also modulates the d-band center of the surface-active atoms that widely help to suppress the competitive HER . The accessibility of free charge carriers is reflected in the conductivity of the semiconductor that reinforces the kinetics of the proton-coupled electron transfer process (NRR) that requires six electrons and six protons to completely get reduced to ammonia, whereas the HER involves much faster kinetics with only two electrons and two protons .…”

Section: Introductionmentioning

confidence: 99%

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Alteration of Electronic Band Structure via a Metal–Semiconductor Interfacial Effect Enables High Faradaic Efficiency for Electrochemical Nitrogen Fixation

Biswas¹,

Nandi

Kamboj³

et al. 2021

ACS Nano

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The interface engineering strategy has been an emerging field in terms of material improvisation that not only alters the electronic band structure of a material but also induces beneficial effects on electrochemical performances. Particularly, it is of immense importance for the environmentally benign electrochemical nitrogen reduction reaction (NRR), which is potentially impeded by the competing hydrogen evolution reaction (HER). The main problem lies in the attainment of the desired current density at a negotiable potential where the NRR would dominate over the HER, which in turn hampers the Faradaic efficiency for the NRR. To circumvent this issue, catalyst development becomes necessary, which would display a weak affinity for H-adsorption suppressing the HER at the catalyst surface. Herein, we have adopted the interfacial engineering strategy to synthesize our electrocatalyst NPG@SnS2, which not only suppressed the HER on the active site but yielded 49.3% F.E. for the NRR. Extensive experimental work and DFT calculations regarded that due to the charge redistribution, the Mott–Schottky effect, and the band bending of SnS2 across the contact layer at the interface of NPG, the d-band center for the surface Sn atoms in NPG@SnS2 lowered, which resulted in favored adsorption of N2 on the Sn active site. This phenomenon was driven even forward by the upshift of the Fermi level, and eventually, a decrease was seen in the work function of the heterostructure that increased the conductivity of the material as compared to pristine SnS2. This strategy thus provides a field to methodically suppress the HER in the realm of improving the Faradaic efficiency for the NRR.

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Section: Resultsmentioning

confidence: 66%

Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Alteration of Electronic Band Structure via a Metal–Semiconductor Interfacial Effect Enables High Faradaic Efficiency for Electrochemical Nitrogen Fixation

Biswas¹,

Nandi

Kamboj³

et al. 2021

ACS Nano

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“…The combination generates an electron density transfer from Pt to the ZIF framework via Pt–N ZIF interaction, which in turn creates electron‐deficient sites on the Pt surface, enabling strong affinity for preferential N 2 adsorption (Figure 13D). 146 DFT simulations also confirm a lower‐energy barrier for N 2 adsorption realized by the coating of ZIF (Figure 13E). An excellent NRR performance with a NH 3 yield rate over 161 μg mg −1 h −1 and a high FE of over 44% is achieved, which is up to 44 times that of the corresponding bare Pt/Au nanosphere (Figure 13F).…”

Section: Electrocatalyst‐level Strategymentioning

confidence: 61%

Comprehensive understanding and rational regulation of microenvironment for gas‐involving electrochemical reactions

Cheng

Wang

et al. 2023

Carbon Energy

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Substantial progress has been made in the understanding of gas‐involving electrochemical reactions recently for the sake of clean, renewable, and efficient energy technologies. However, the specific influence mechanism of the microenvironment at the reaction interface on the electrocatalytic performance (activity, selectivity, and durability) remains unclear. Here, we provide a comprehensive understanding of the interfacial microenvironment of gas‐involving electrocatalysis, including carbon dioxide reduction reaction and nitrogen reduction reaction, and classify the factors affecting the reaction thermodynamics and kinetics into gas diffusion, proton supply, and electron transfer. This categorization allows a systematic survey of the literature focusing on electrolyzer‐level (optimization of the device, control of the experimental condition, and design of the working electrode), electrolyte‐level (increase of gas solubility, regulation of proton supply, and substitution of anodic reaction), and electrocatalyst‐level strategies (promotion of gas affinity, adjustment of hydrophobicity, and enhancement of conductivity), aiming to retrieve the correlations between the microenvironment and electrochemical performance. Finally, priorities for future studies are suggested to support the comprehensive improvement of next‐generation gas‐involving electrochemical reactions.

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“…It elucidated that the valence electrons in Fe(II)Cu(II)Fe(III)-LDH were readily excited. [48] To uncover the electronic structures of as-developed catalysts, the DFT calculations were conducted (for calculation To probe the adsorptive property on catalyst surface, the d-band model, which reflected the adsorption strength between catalyst and adsorbate to the catalyst d-band center position, [49] was further investigated. As shown in Figure 3e, the total d-band center of Cu(II)Fe(III)-LDH is located at −5.54 eV.…”

Section: Resultsmentioning

confidence: 99%

Engineering Reductive Iron on a Layered Double Hydroxide Electrocatalyst for Facilitating Nitrogen Reduction Reaction

Kong

et al. 2022

Adv Materials Inter

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new catalysts to decrease the utilization of noble metal while simultaneously maintaining efficient nitrogen fixation performance becomes an important tendency in this field. [15][16][17][18][19] Chemists have suggested that lowvalence metal species with electron-rich characteristics play an essential role in catalytic process. [20] For instance, Ti (III), [21] Fe (II), [22] Cu (I), [23] Co (II), [24] Mn (III), [25] Ni (I), [26] and Zn (I) [27] act as catalytic centers or impetuses to facilitate the kinetics of multifarious thermodynamically unfavorable processes, including water splitting and nitrogen reduction. Among these low-valence nonprecious 3d transition metals (3d TMs), Fe desires particular attention. [28,29] As one of the cheapest and most abundant metals on the earth, Fe also exists in biological nitrogenases for natural N 2 fixation. [30] The Fe compounds have been widely utilized as catalysts for artificial N 2 fixation in the Haber-Bosch and electrochemical reactions, [31] endowing Fe-based catalysts with immense potential for electrocatalytic NRR under ambient conditions.Recently, layered double hydroxides (LDHs), one kind of 2D nanomaterials, have emerged as promising candidates of NRR electrocatalysts due to their adjustability of morphology, electronic structure, and composition. [32,33] However, the poor conductivity and weak nitrogen activation ability of LDHs handicap their electrocatalytic activities in ammonia synthesis. Numerous research focused on doping a transition metal electrocatalyst by heteroatoms, such as boron, phosphorus, or copper, which could generate defects or adjust electronic structure to improve the NRR activity. [34][35][36] Previous work have also proved that the unsaturated metal sites with electron-rich properties could boost nitrogen absorption, lower the reaction energy barrier, thus leading to an high NH 3 yield as well as FE. [37] According to Lewis acid-base theory, the dinitrogen molecule is a soft base that inclines to react with soft acid. Theoretical and experimental results demonstrated that low-valence 3d TMs could serve as Lewis acid sites. It will be in favor of the adsorption and activation of nitrogen, thereby promoting the catalytic performance. [38,39] Nevertheless, there lacks of attempts on Fe-based LDHs catalysts engineered low-valence metals, inspiring in-depth study.Herein, ferrous iron replacing copper layered double hydroxide (Fe(II)Cu(II)Fe(III)-LDH) was successfully synthesized by a modified solvothermal method. In neutral media, the catalyst reached Ammonia is an indispensable chemical, of which the industrial production is still dominated by Haber-Bosch process operated at harsh conditions. The ecofriendly electrocatalytic N 2 reduction reaction (NRR) emerges as an alternative, however, such technique currently suffers from tough dynamics on account of difficulties in the adsorption or protonation of N 2 on catalysts. To eliminate the obstacle, a simple and valid strategy of ferrous iron replacing copper is proposed to regulate the electron...

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ZIF‐Induced d‐Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

Cited by 32 publications

References 34 publications

Alteration of Electronic Band Structure via a Metal–Semiconductor Interfacial Effect Enables High Faradaic Efficiency for Electrochemical Nitrogen Fixation

Alteration of Electronic Band Structure via a Metal–Semiconductor Interfacial Effect Enables High Faradaic Efficiency for Electrochemical Nitrogen Fixation

Comprehensive understanding and rational regulation of microenvironment for gas‐involving electrochemical reactions

Engineering Reductive Iron on a Layered Double Hydroxide Electrocatalyst for Facilitating Nitrogen Reduction Reaction

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