Deciphering the active origin for urea oxidation reaction over nitrogen penetrated nickel nanoparticles embedded in carbon nanotubes

Zhao, Zhanhong; Wang, Haidong; Tan, Hengfeng; Wu, Xinfeng; Kang, Yuxin; Dong, Yinrui; Li, Xingyun; Jin, Shengming; Chang, Xinghua

doi:10.1016/j.jcis.2022.06.131

Cited by 10 publications

(4 citation statements)

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“…This low value suggests that the kinetic rate slightly depends on the urea concentration, which can be explained by these assumptions: (i)the strong affinity of urea to the nickel peroxide particles. Several works have studied the adsorption of urea molecules on various adsorbents: nickel(II) oxide NiO, 43 nickel nanoparticles embedded in carbon nanotubes, 44 and nickel(III) sites 45 . Whatever the adsorbent nature, a strong affinity of urea with nickel 43 and a low adsorption energy of urea 46 have been reported.…”

Section: Results On the Kinetic Of The Catalytic Indirect Urea Oxidationmentioning

confidence: 99%

Indirect urea electrooxidation by nickel(III) in alkaline medium: From kinetic and mechanism to reactor modeling

et al. 2023

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This study consists in the determination of two kinetic laws of urea oxidation (UO) and electrooxidation (UEO) in alkaline media on nickel(III). Two kinds of active sites were examined, the first one derived from a Ni(OH)2 powder and the second from a massive nickel electrode. Partial orders of nickel(III) (two for UO and five UEO) enable to conclude about (i) the urea adsorption on two nickel(III) sites and (ii) that a multistep oxidation of urea occurs involving five nickel(III) site electroregenerations. A multipathway mechanism is also proposed to explain UEO facilitated by the nickel(III)/nickel(II) mediation system, and to predict the by‐products' formation previously identified (). At last, a model combining the UEO kinetic law previously established, with diffusive and convective transport phenomena was developed. A consistent correlation (maximum deviation of 6%) between laboratory electrolysis results with the model' predictions was obtained under different operating conditions, enabling the validation of this model.

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Section: Results On the Kinetic Of The Catalytic Indirect Urea Oxidationmentioning

confidence: 99%

Indirect urea electrooxidation by nickel(III) in alkaline medium: From kinetic and mechanism to reactor modeling

et al. 2023

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“…Additionally, the binding energy of Ni 0 for Ni@DC-0.03, Ni@DC-0.04, Ni@DC-0.05, and Ni@DC-0.06 is 852.1, 852.4, 852.7, and 853.2 eV, respectively. The upward shift indicates that the electronic environment of Ni is regulated by the electron shift from Ni to the defective carbon species. − Furthermore, as seen in Figure b, the C 1s peaks at 285.7 and 289.8 eV are related to C–O and CO 3 2– groups, respectively, , indicating that the carbon layer surface is rich in oxygen-containing functional groups. It is noteworthy that the strongest signal peaks are all around the binding energy (BE) of 284.0 eV, demonstrating that the carbon layer of the Ni@DC- x is always dominated by sp 2 , and the carbon layer is rich in defects. , In detail, the binding energies of sp 2 C for Ni@DC-0.03, Ni@DC-0.04, Ni@DC-0.05, and Ni@DC-0.06 are 284.2, 283.9, 283.6, and 283.2 eV, respectively, suggesting that the binding energy of sp 2 C decreases with the increment of carbon defects.…”

Section: Resultsmentioning

confidence: 97%

Decarboxylation-Induced Defects in MOF-Derived Ni@C Catalysts for Efficient Chemoselective Hydrogenation of Nitrocyclohexane to Cyclohexanone Oxime

et al. 2023

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In this work, MOF-derived Ni@C catalysts with rich defects were synthesized using a facile thermally decarboxylation-induced defect strategy for nitrocyclohexane (NCH) hydrogenation. It was found that the strong metal–support interaction (SMSI) between the defect-rich carbon and Ni promotes the dispersion of Ni nanoparticles, reduces the Ni particle size, and affects the surface charge state of Ni to form electron-deficient Ni, thus exhibiting outstanding catalytic activity. Additionally, in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) illustrates that the transformation path of nitrosocyclohexane (N-NCH) is critical for obtaining high selectivity to cyclohexanone oxime (CHO). Furthermore, the density functional theory (DFT) calculations confirm that the SMSI between the defect-rich carbon and Ni leads to the formation of electron-deficient Ni with a lower d-band center, which can weaken the adsorption of N-NCH and CHO, enhance the adsorption of N-cyclohexylhydroxylamine (N-CHH) and cyclohexylamine (CHA), reduce the reaction energy of the N-NCH to CHO, and increase the reaction energy of the N-NCH to CHA, thus showing the highest selectivity to CHO. Under optimum conditions, Ni@DC-0.06 gives 97.2% selectivity to CHO at 95.2% NCH conversion.

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“…5b), typically due to the inception of strongly adsorbed intermediates. [44][45][46][47] This observation may explain the discernable passivation effect noticed in Ni(OH) 2 -gPF, 45 evidencing that selfassembled c-oriented Ni(OH) 2 lms prociently mitigate the genesis of such intermediates and the passivation trend.…”

Section: Electrochemical Testsmentioning

confidence: 99%

Self-assembled c-oriented Ni(OH)₂ films for enhanced electrocatalytic activity towards the urea oxidation reaction

Dong,

Peng,

Zhao

et al. 2023

RSC Adv.

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Deciphering the active origin for urea oxidation reaction over nitrogen penetrated nickel nanoparticles embedded in carbon nanotubes

Cited by 10 publications

References 50 publications

Indirect urea electrooxidation by nickel(III) in alkaline medium: From kinetic and mechanism to reactor modeling

Indirect urea electrooxidation by nickel(III) in alkaline medium: From kinetic and mechanism to reactor modeling

Decarboxylation-Induced Defects in MOF-Derived Ni@C Catalysts for Efficient Chemoselective Hydrogenation of Nitrocyclohexane to Cyclohexanone Oxime

Self-assembled c-oriented Ni(OH)₂ films for enhanced electrocatalytic activity towards the urea oxidation reaction

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Deciphering the active origin for urea oxidation reaction over nitrogen penetrated nickel nanoparticles embedded in carbon nanotubes

Cited by 10 publications

References 50 publications

Indirect urea electrooxidation by nickel(III) in alkaline medium: From kinetic and mechanism to reactor modeling

Indirect urea electrooxidation by nickel(III) in alkaline medium: From kinetic and mechanism to reactor modeling

Decarboxylation-Induced Defects in MOF-Derived Ni@C Catalysts for Efficient Chemoselective Hydrogenation of Nitrocyclohexane to Cyclohexanone Oxime

Self-assembled c-oriented Ni(OH)2 films for enhanced electrocatalytic activity towards the urea oxidation reaction

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Product

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Self-assembled c-oriented Ni(OH)₂ films for enhanced electrocatalytic activity towards the urea oxidation reaction