A-site deficient perovskite with nano-socketed Ni-Fe alloy particles as highly active and durable catalyst for high-temperature CO2 electrolysis

Ding, Shaochen; Li, Meng; Pang, Wanying; Hua, Bin; Duan, Nanqi; Zhang, Yaqian; Zhang, Shengnian; Jin, Zhehui; Luo, Jing‐Li

doi:10.1016/j.electacta.2020.135683

Cited by 51 publications

(33 citation statements)

References 39 publications

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“…This is because in mixed cation systems, the Gibbs energy of reduction is a function of the strength of the metal‐oxygen bonds of both substituted metals and hence the energy can be decreased by introducing more reducible ions (Figure 2 d). [11c–e] Besides, it is also reported that doping of Co increases the total energy of the perovskite system and the Co−Fe bond would form more easily than the Fe−Fe bond due to the lower formation energy, which also accounts for the promoting effects of Co on the Fe exsolution [11f] …”

Section: Mechanism Of Alloy Exsolutionmentioning

confidence: 99%

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Trends and Prospects of Bimetallic Exsolution

Tang

Kousi

Neagu

et al. 2021

Chemistry A European J

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Supported bimetallic nanoparticles used for various chemical transformations appear to be more appealing than their monometallic counterparts, because of their unique properties mainly originating from the synergistic effects between the two different metals. Exsolution, a relatively new preparation method for supported nanoparticles, has earned increasing attention for bimetallic systems in the past decade, not only due to the high stability of the resulting nanoparticles but also for the potential to control key particle properties (size, composition, structure, morphology, etc.). In this review, we summarize the trends and advances on exsolution of bimetallic systems and provide prospects for future studies in this field.

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Section: Mechanism Of Alloy Exsolutionmentioning

confidence: 99%

“…(d) Segregation energies of B‐site metals from LaCr 0.5 Fe 0.5 O 3 (LCFO) and Ni‐doped LCFO (LCFNO). Adapted with permission [11d] …”

Section: Mechanism Of Alloy Exsolutionmentioning

confidence: 99%

Trends and Prospects of Bimetallic Exsolution

Tang

Kousi

Neagu

et al. 2021

Chemistry A European J

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“…For instance, Ni/YSZ-based SOEC cathodes require significant supplemental potentials (overpotentials of >0.3 V) in addition to the thermodynamic potential (∼1 V at 1073 K) to overcome the thermal and cell overpotential requirements for electrochemical reduction of CO 2 to CO. One of the contributing factors is the activation overpotential related to the inefficiency of the electrocatalyst to activate CO 2 . , To overcome this issue, many efforts have been reported on designing alternative cathode electrocatalysts to replace the traditional Ni/YSZ cermets. For instance, experimental studies involving the use of either supported or exsolved Ni and/or Fe-based alloys as electrocatalysts have demonstrated to lead to improved electrolysis performance. − However, catalytic insights on the effects that these alloy electrocatalysts induce on CO 2 reduction are scarce and mainly restricted to theoretical studies. , Using density functional theory (DFT) calculations, we previously reported that oxygen binding energy on transition metals was a promising descriptor in predicting their activity for electrochemical CO 2 reduction in SOECs . We suggested that among the nonprecious metals, Co and Fe would be catalytically more active than Ni because of their optimal binding of oxygen.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Reduction of CO₂ on Metal-Based Cathode Electrocatalysts of Solid Oxide Electrolysis Cells

Carneiro

Tezel

et al. 2020

Ind. Eng. Chem. Res.

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Electrochemical reduction of CO2 using solid oxide electrolysis cells (SOECs) has emerged as an attractive approach for converting CO2 to high energy molecules, such as CO, a key precursor for the synthesis of fuels and chemicals using the commercially established Fischer–Tropsch process. The in situ generation of syngas (CO and H2) has also been demonstrated in SOECs through the coelectrolysis of CO2 and H2O. However, conventional Ni-based SOEC cathodes exhibit high overpotential losses associated with CO2 activation, leading to the disproportional activation of CO2 and H2O during coelectrolysis, facilitating the equilibrium-limited thermochemical reverse water gas shift (RWGS) reaction. Thus, identification of factors that govern CO2 activation on transition metal electrocatalysts is important toward optimizing the performance of SOEC cathodes for modulated production of syngas. Herein, we experimentally assess the electrocatalytic performance of monometallic transition metal electrocatalysts (Fe, Ni, and Pd) toward electrochemical CO2 reduction in SOECs with the aim of understanding the electrocatalyst characteristics that govern this performance. We report that metal oxophilicity (a property correlated to the strength of metal–oxygen bonding) plays an important role in the energetics associated with electrochemical CO2 reduction and electrocatalyst deactivation via oxidation. We suggest that a compromise in the oxophilicity of the metal is required to achieve optimal electrochemical activity and stability because CO2 activation is facile on highly oxophilic transition metals to the left of Ni (i.e., Fe); however, strong oxygen binding on these metals leads to their deactivation via oxidation. Potential approaches that facilitate the electronic structure modulation of transitional metals to optimize their surface oxophilicity, such as alloying, are suggested.

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“…Moreover, a more comprehensive comparison by the DFT simulation also shows that various metal components are thermodynamically more favorable to in situ exsolve from the γ-NiOOH as compared to their counterparts from perovskites. [25,[41][42][43] The segregation energy of in situ exsolving Cu and other transition metals (Mn, Fe, Co) from the γ-NiOOH framework (Figure 5E) is lower or on par with most exsolving atoms in perovskite frameworks. This suggests that similar exsolution approaches can be easily performed with a wide range of elements to form different NPs.…”

Section: General Applicabilitymentioning

confidence: 99%

A Robust Approach to In Situ Exsolve Highly Dispersed and Stable Electrocatalysts

Wang

Zhang

Ding

et al. 2022

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Catalysts made of in situ exsolved metal nanoparticles often demonstrate promising activity and high stability in many applications. However, the traditional approach is limited by perovskites as prevailing precursor and requires high temperature typically above 900 K. Here, with the guidance of theoretical calculation, an unprecedented and substantially facile technique is demonstrated for Cu nanoparticles exsolved from interstitially Cu cations doped nickel‐based hydroxide, which is accomplished swiftly at room temperature and results in metal nanoparticles with a quasi‐uniform size of 4 nm, delivering an exceptional CO faradaic efficiency of 95.6% for the electrochemical reduction of CO2 with a notable durability. This design principle is further proven to be generally applicable to other metals and foregrounded for guiding the development of advanced catalytic materials.

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A-site deficient perovskite with nano-socketed Ni-Fe alloy particles as highly active and durable catalyst for high-temperature CO2 electrolysis

Cited by 51 publications

References 39 publications

Trends and Prospects of Bimetallic Exsolution

Trends and Prospects of Bimetallic Exsolution

Electrochemical Reduction of CO₂ on Metal-Based Cathode Electrocatalysts of Solid Oxide Electrolysis Cells

A Robust Approach to In Situ Exsolve Highly Dispersed and Stable Electrocatalysts

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A-site deficient perovskite with nano-socketed Ni-Fe alloy particles as highly active and durable catalyst for high-temperature CO2 electrolysis

Cited by 51 publications

References 39 publications

Trends and Prospects of Bimetallic Exsolution

Trends and Prospects of Bimetallic Exsolution

Electrochemical Reduction of CO2 on Metal-Based Cathode Electrocatalysts of Solid Oxide Electrolysis Cells

A Robust Approach to In Situ Exsolve Highly Dispersed and Stable Electrocatalysts

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Product

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Electrochemical Reduction of CO₂ on Metal-Based Cathode Electrocatalysts of Solid Oxide Electrolysis Cells