Benzaldoxime to benzamide rearrangement catalysed by rhodium(III) hydroxocomplexes: The influence of polynuclear species

Berdyugin, Semen; Volchek, Victoria V.; Asanova, Tatyana; Kolesov, B. A.; Gerasimov, Evgeny Yu.; Filatov, E. Yu.; Vasilchenko, Danila; Korenev, S. V.

doi:10.1016/j.apcata.2019.117242

Cited by 6 publications

(6 citation statements)

References 35 publications

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“…We then performed in situ surface‐enhanced Raman scattering spectroscopy (in situ SERS), aiming to determine fingerprint spectrum differences in the COOR mechanism between the two catalysts 47–49 . Au flakes especially treated with KCl solution were used as the catalyst substrates to efficiently enhance the Raman signal of the reaction intermediates 50,51 .…”

Section: Resultsmentioning

confidence: 99%

“…We then performed in situ surface-enhanced Raman scattering spectroscopy (in situ SERS), aiming to determine fingerprint spectrum differences in the COOR mechanism between the two catalysts. [47][48][49] Au flakes especially treated with KCl solution were used as the catalyst substrates to efficiently enhance the Raman signal of the reaction intermediates. 50,51 Direct spectroscopic signals were collected in a N 2or CO-saturated 0.1 M HClO 4 solution, to differentiate the water activation process from the CO oxidation process.…”

Section: Reaction Mechanism Probingmentioning

confidence: 99%

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The decisive role of adsorbed OH* in low‐potential CO electro‐oxidation on single‐atom catalytic sites

Xian

Wang

et al. 2023

Carbon Energy

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CO impurity‐induced catalyst deactivation has long been one of the biggest challenges in proton‐exchange membrane fuel cells, with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catalytic site. Here, we present a mechanistic study that overturns this understanding by using Rh‐based single‐atom catalysis centers as model catalysts. We precisely modulated the chelation structure of the Rh catalyst by coordinating Rh with C or N atoms, and probed the reaction mechanism by surface‐enhanced Raman spectroscopy. Direct spectroscopic evidence for intermediates indicates that the reactivity of adsorbed OH*, rather than the adsorption strength of CO*, dictates the CO electrocatalytic oxidation behavior. The RhN4 sites, which adsorb the OH* intermediate more weakly than RhC4 sites, showed prominent CO oxidation activity that not only far exceeded the traditional Pt/C but also the RhC4 sites with similar CO adsorption strength. From this study, it is clear that a paradigm shift in future research should be considered to rationally design high‐performance CO electro‐oxidation reaction catalysts by sufficiently considering the water‐related reaction intermediate during catalysis.

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Section: Resultsmentioning

confidence: 99%

Section: Reaction Mechanism Probingmentioning

confidence: 99%

The decisive role of adsorbed OH* in low‐potential CO electro‐oxidation on single‐atom catalytic sites

Xian

Wang

et al. 2023

Carbon Energy

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“…Primary amides are an extensive group of chemicals broadly utilized as intermediates in various organic syntheses and in industrial applications such as detergents, lubricants, engineering plastics and pharmaceuticals 18–20 . Although ketoximes rearrangement by use of acids ensures the formation of amides in high yield, aldoximes form the corresponding nitriles rather than forming the primary amides 21–23 . Hence, designing an efficient catalytic system for primary amides synthesis from aldoximes is of significant importance.…”

Section: Introductionmentioning

confidence: 99%

Green synthesis of reduced graphene oxide anchored Fe₃O₄‐Pd hetero‐nanostructure: An efficient, magnetically separable and reusable catalyst for Beckmann rearrangement of aldoximes to amides

Hazarika,

Borah

2023

Applied Organom Chemis

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The multifaceted Fe3O4‐Pd@rGO nanocomposite (NC) has been synthesized successfully by a biogenic method using Ocimum tenuiflorum leaf extract. The preparation of graphene oxide (GO) was done by the well‐known modified Hummer method. The as‐synthesized Fe3O4‐Pd@rGO NC was extensively characterized by various analytical techniques, namely, Fourier transform infrared (FTIR), X‐ray diffraction (XRD), field emission scanning electron microscopy‐energy‐dispersive X‐ray spectroscopy (FESEM‐EDX), high‐resolution transmission electron microscopy (HRTEM), inductively coupled plasma‐atomic emission spectrometry (ICP‐AES), X‐ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM) and Brunauer–Emmett–Teller (BET) surface area analysis. The absence of peak corresponding to υ(CO) at 1732 cm−1 in the FTIR spectrum of Fe3O4‐Pd@rGO enumerates the reduction of GO to reduced graphene oxide (rGO) during Fe3O4‐Pd nanoparticle (NP) synthesis with O. tenuiflorum leaf extract. The XRD pattern reveals the existence of rGO, cubic‐phased spinel‐structured Fe3O4 along with the formation of metallic Pd NP without any impurities. The FESEM image designates the spherical and flake‐like morphology of the NC. The crystallite size of the NC was calculated employing the Debye–Scherrer equation and was found to be 3.45 nm corresponding to the (220) plane. The average particle size of Fe3O4‐Pd NPs as estimated from the particle size distribution curve was ascertained as 3.03 nm. The utmost saturation magnetization value of the NC as evaluated by VSM study has appeared at 0.6219 emu g−1 having coercivity value of 335.1 Oe and remanent magnetization value of 0.0767 emu g−1, suggesting the existence of a ferromagnetic material in the synthesized NC. It was a stable and highly efficient catalyst for Beckmann rearrangement of aldoximes using in an environment‐friendly medium. It afforded up to 99% isolated yield of the preferred products under acid‐free condition, avoiding the use of any harsh chemicals that will be beneficial for future industrial applications. Finally, the magnetic component of the NC allowed for easy recovery of the catalyst, thereby eliminating the chance of leaching of metal atoms, and was reusable till six successive cycles without apparent loss of its catalytic performance.

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“…The low-temperature preparation of binary alloys from single-source precursors has been studied in a large number of works in the last decade [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Binary alloys can be prepared for a large variety of refractory metals including Pt, Pd, Ir, Rh, and Os.…”

Section: Introductionmentioning

confidence: 99%

“…The application of alloys with carbide-forming elements might be the next step for the design of multicomponent refractory ultrahard materials [21]. Nevertheless, systems with refractory metals such as Mo, W, and Ta have barely been investigated due to their high affinity to oxygen and the difficulties they present in being reduced from MO 4 2− anions that are stable in water solutions. In the current study, we report an investigation of [NiEn 3 ](MoO 4 ) 0.5 (WO 4 ) 0.5 (En = ethylenediamine, H 2 NCH 2 CH 2 NH 2 ) which can be obtained by the co-crystallization of two individual isoformular complex salts [NiEn 3 ]WO 4 and [NiEn 3 ]MoO 4 .…”

Section: Introductionmentioning

confidence: 99%

[NiEn3](MoO4)0.5(WO4)0.5 Co-Crystals as Single-Source Precursors for Ternary Refractory Ni–Mo–W Alloys

et al. 2021

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The co-crystallisation of [NiEn3](NO3)2 (En = ethylenediamine) with Na2MoO4 and Na2WO4 from a water solution results in the formation of [NiEn3](MoO4)0.5(WO4)0.5 co-crystals. According to the X-ray diffraction analysis of eight single crystals, the parameters of the hexagonal unit cell (space group P–31c, Z = 2) vary in the following intervals: a = 9.2332(3)–9.2566(6); c = 9.9512(12)–9.9753(7) Å with the Mo/W ratio changing from 0.513(3)/0.487(3) to 0.078(4)/0.895(9). The thermal decomposition of [NiEn3](MoO4)0.5(WO4)0.5 individual crystals obtained by co-crystallisation was performed in He and H2 atmospheres. The ex situ X-ray study of thermal decomposition products shows the formation of nanocrystalline refractory alloys and carbide composites containing ternary Ni–Mo–W phases. The formation of carbon–nitride phases at certain stages of heating up to 1000 °C were shown.

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Benzaldoxime to benzamide rearrangement catalysed by rhodium(III) hydroxocomplexes: The influence of polynuclear species

Cited by 6 publications

References 35 publications

The decisive role of adsorbed OH* in low‐potential CO electro‐oxidation on single‐atom catalytic sites

The decisive role of adsorbed OH* in low‐potential CO electro‐oxidation on single‐atom catalytic sites

Green synthesis of reduced graphene oxide anchored Fe₃O₄‐Pd hetero‐nanostructure: An efficient, magnetically separable and reusable catalyst for Beckmann rearrangement of aldoximes to amides

[NiEn3](MoO4)0.5(WO4)0.5 Co-Crystals as Single-Source Precursors for Ternary Refractory Ni–Mo–W Alloys

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Benzaldoxime to benzamide rearrangement catalysed by rhodium(III) hydroxocomplexes: The influence of polynuclear species

Cited by 6 publications

References 35 publications

The decisive role of adsorbed OH* in low‐potential CO electro‐oxidation on single‐atom catalytic sites

The decisive role of adsorbed OH* in low‐potential CO electro‐oxidation on single‐atom catalytic sites

Green synthesis of reduced graphene oxide anchored Fe3O4‐Pd hetero‐nanostructure: An efficient, magnetically separable and reusable catalyst for Beckmann rearrangement of aldoximes to amides

[NiEn3](MoO4)0.5(WO4)0.5 Co-Crystals as Single-Source Precursors for Ternary Refractory Ni–Mo–W Alloys

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Product

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Green synthesis of reduced graphene oxide anchored Fe₃O₄‐Pd hetero‐nanostructure: An efficient, magnetically separable and reusable catalyst for Beckmann rearrangement of aldoximes to amides