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

Yuan, Pei; Liao, Xiaoqing; Cui, Haishuai; Hao, Fang; Xiong, Wei; Luo, He’an; Lv, Yang; Liu, Pingle

doi:10.1021/acscatal.2c05504

Cited by 15 publications

(3 citation statements)

References 67 publications

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“…In situ DRIFTS can be used to study the adsorption, activation, and desorption processes of substrate molecules. , The detailed procedures are described in the Supporting Information (Text S3). The in situ DRIFTS result of MOF-808-S in Figure shows that the orbital peak at 1718 cm –1 is ascribed to ν(CO) of acrolein, and the orbital peak at 1475 cm –1 belongs to ν(CC). , Note that MOF-808-S exhibits a significant red shift at the ν (CO) orbitals in comparison with the gaseous acrolein.…”

Section: Results and Discussionmentioning

confidence: 99%

Highly Efficient Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols over Defective MOF-808 with Constructed Frustrated Lewis Pairs

Zhong,

Liao,

Cui

et al. 2024

ACS Catal.

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Solid frustrated Lewis pair (FLP) catalysts have received much attention. In this work, MOF-808 with rich defects was constructed using a facile monocarboxylic acid modulatorinduced defect strategy and applied in the transfer hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohol using cyclohexanol as the hydrogen source. MOF-808 was prepared from different zirconium precursors, and it was found that MOF-808-ZT obtained from ZrCl 4 and H 3 BTC forms abundant surface hydroxyl groups (Zr−OH, base sites). Moreover, MOF-808-PA with missing linker defects was constructed by introducing monocarboxylic acid to preoccupy the coordination sites of MOF-808-ZT, leading to abundant Zr−OH 2 . The coordinated water molecules are removed by the dehydration of MOF-808-PA at 180 °C, and the underlying coordinatively unsaturated Zr 4+ (Zr-CUS) is exposed and acts as a Lewis acid site. Characterizations and DFT calculations show that the Zr-CUS/Zr−OH FLPs sites can efficiently activate the C�O of aldehydes and −OH of cyclohexanol and reduce their activation energy barrier, thus exhibiting good catalytic performance. Moreover, these FLP sites can easily easily dissociate the H−H bond with a lower activation energy of 0.15 eV, thereby achieving a better catalytic reactivity in the direct hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols. A possible reaction mechanism was proposed based on in situ DRIFT, vacuum FTIR, and DFT calculations.

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Section: Results and Discussionmentioning

confidence: 99%

Highly Efficient Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols over Defective MOF-808 with Constructed Frustrated Lewis Pairs

Zhong,

Liao,

Cui

et al. 2024

ACS Catal.

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“…Yao prepared activated carbon-supported non-noble bimetallic Ni–Cu for NCH hydrogenation to CHO with 87.5% yield and found that Cu could effectively promote Ni nanoparticle dispersion and facilitate Ni 0 formation . Recently, our group synthesized MOF-derived Ni@C catalysts with rich defects and the strong metal–support interaction (SMSI) between the defect-rich carbon and Ni promotes Ni nanoparticles dispersion, reduces the Ni particle size, and affects the surface charge state of Ni to form electron-deficient Ni, hence exhibited outstanding catalytic performance in NCH hydrogenation to CHO . However, MOFs have the disadvantages of complex preparation and high cost.…”

Section: Introductionmentioning

confidence: 99%

“…11 Recently, our group synthesized MOF-derived Ni@C catalysts with rich defects and the strong metal−support interaction (SMSI) between the defect-rich carbon and Ni promotes Ni nanoparticles dispersion, reduces the Ni particle size, and affects the surface charge state of Ni to form electron-deficient Ni, hence exhibited outstanding catalytic performance in NCH hydrogenation to CHO. 12 However, MOFs have the disadvantages of complex preparation and high cost.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Hydrogenation of Nitrocyclohexane to Cyclohexanone Oxime over NiTi-Layered Double Hydroxide: The Key Role of Oxygen Vacancies

Zhang,

Liao,

Cui

et al. 2023

ACS Sustainable Chem. Eng.

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Highly efficient selective hydrogenation of nitrocyclohexane (NCH) to cyclohexanone oxime (CHO) is important for the production of caprolactam. In this work, NiTi catalysts (NiTi-IMP, NiTi-HDT, and NiTi-LDH) were prepared by different methods and applied in NCH hydrogenation to CHO. It was found that NiTi-LDH with rich oxygen vacancies (Ov) induces a strong metal−support interaction (SMSI) between Ni and TiO 2 , hence favoring the dispersion of Ni nanoparticles, promoting the reduction of NiO and the formation of much more metallic Ni, and facilitating the electron transfer between Ni and Ti. In situ DRIFTS reveals the mechanism for NCH hydrogenation on Ov-rich NiTi-LDH, showing that Ov benefits the enhancement of NCH conversion and suppresses overhydrogenation to the byproducts of cyclohexanone (CHone) and cyclohexylamine (CHA). Moreover, density functional theory (DFT) calculations illustrate that Ov facilitates the adsorption of NCH and desorption of CHO, favors the α-H transfer of nitrosocyclohexane (N−CHH) to CHO, and significantly reduces the overall reaction energy barrier of NCH to CHO. Under optimum conditions, NiTi-2 with the largest amount of Ov gives 90.71% selectivity to CHO at 99.84% NCH conversion. This study provides an efficient and economical catalyst for the preparation of CHO from NCH, and it is valuable for promoting the industrial production of caprolactam toward resource conservation and environment friendliness.

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Photocatalytic Partial Water Oxidation Promoted by a Hydrogen Acceptor‐Hydroxyl Mediator Couple

Mai,

Zhang,

Maliutina

et al. 2024

Advanced Science

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Hydrogen peroxide (H2O2) is an important chemical in synthetic chemistry with huge demands. Photocatalytic synthesis of H2O2 via oxygen reduction and water oxidation reactions (ORR and WOR) is considered as a promising and desirable solution for on‐site applications. However, the efficiency of such a process is low due to the poor solubility of molecular oxygen and the rapid reverse reaction of hydroxyl radicals (•OH) with hydrogen atoms (H). Here, a strategy is proposed to boost the H2O2 evolution via oxidation of water by employing a H acceptor (A, nitrocyclohexane), an •OH mediator (M, dioxane), and a photocatalyst (CdS nanosheets). While •OH radicals are stabilized by dioxane to produce ketyl radicals prior to the formation of H2O2, H atoms are effectively utilized in the generation of cyclohexanone oxime, an important intermediate in the production of Nylon 6. The system displays a rapid kinetic accumulation of H2O2 (0.13 min−1) to a high concentration (6.6 mM). At optimum reaction conditions, a high quantum efficiency (16.6%) and light‐to‐chemical conversion efficiency (4.9%) can be achieved under 410 nm irradiation.

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

Cited by 15 publications

References 67 publications

Highly Efficient Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols over Defective MOF-808 with Constructed Frustrated Lewis Pairs

Highly Efficient Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols over Defective MOF-808 with Constructed Frustrated Lewis Pairs

Highly Efficient Hydrogenation of Nitrocyclohexane to Cyclohexanone Oxime over NiTi-Layered Double Hydroxide: The Key Role of Oxygen Vacancies

Photocatalytic Partial Water Oxidation Promoted by a Hydrogen Acceptor‐Hydroxyl Mediator Couple

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