Construction of isolated Ni sites on nitrogen-doped hollow carbon spheres with Ni–N3 configuration for enhanced reduction of nitroarenes

Bao, Feng; Guo, Rou; Cai, Qiulan; Song, Yaping; Li, Nan; Fu, Yanghe; Chen, De-Li; Zhu, Weidong; Zhang, Fumin

doi:10.1007/s12274-022-4290-x

Cited by 21 publications

(10 citation statements)

References 70 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, it is thermodynamically more favorable for the dissociated H1 atom binding to single Ni active site and thus Ni−N 3 -Gr is a reasonable model. It is necessary to note that the transfer hydrogenation reaction of furfural using zeolites 24,26 or ZrO 2 17,18 relies on the cooperation of Lewis acid (Zr) and base (O) sites, very different from the single active site of Ni-SAC in this study and the previously reported SACs for hydrogenation reactions, 41,63,64 where the single atoms act as both Lewis acid and base sites.…”

Section: Theoretical Methods and Modelsmentioning

confidence: 83%

Mechanism of Catalytic Transfer Hydrogenation for Furfural Using Single Ni Atom Catalysts Anchored to Nitrogen-Doped Graphene Sheets

et al. 2022

Self Cite

View full text Add to dashboard Cite

Catalytic transfer hydrogenation (CTH) of α,β-unsaturated aldehydes using single metal atom catalysts supported on nitrogen-incorporated graphene sheet (M–N x -Gr) materials has attracted increasing attention recently, yet the reaction mechanism remains to be explored. Compared to the Ni–N4-Gr model in which the dissociation of isopropanol is highly unfavorable as a result of steric hindrance and inertness of the Ni–N4 site embedded in graphene, the Ni–N3 site in Ni–N3-Gr is more active and facilitates the formation of *H with isopropanol as the H donor, where the dissociation of H from isopropanol with an energy barrier of 0.83 eV is the rate-determining step. An alternative reaction path starts from the coadsorption of isopropanol and furfural molecules at the Ni–N3 site, followed by a direct hydrogen transfer between the two molecules; however, the rate-determining step has a much higher energy barrier of 1.32 eV. Our calculations suggest that the hydrogenation of the aldehyde group is kinetically more favorable than the CC hydrogenation, revealing the high chemoselectivity of furfural to furfuryl alcohol. Our investigations reveal that the CTH mechanism using the Ni–N3-Gr catalyst is different from that on traditional metal oxides, where the former has only one single active site, while two active sites are required for the latter. The proposed reaction mechanism of CTH for furfural in this study should be helpful to guide the design of single metal atom catalysts with appropriate N coordination for application in chemoselective hydrogenation reactions.

show abstract

Section: Theoretical Methods and Modelsmentioning

confidence: 83%

Mechanism of Catalytic Transfer Hydrogenation for Furfural Using Single Ni Atom Catalysts Anchored to Nitrogen-Doped Graphene Sheets

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…The catalytic reduction of nitroaromatics to the corresponding aromatic amines is one of the most important reactions, as aromatic amines are essential organic intermediates for a variety of high-value chemicals such as perfumes, plastics, pharmaceuticals, and pesticides. − Recently, it has been reported that the reduction of nitroaromatics can be facilitated at room temperature in the presence of NaBH 4 . , Nowadays, catalysts based on noble metals (Ru, Pd, Ag, Pt, Au, etc.) are widely utilized for the reduction of nitroaromatics due to their high catalytic activity .…”

Section: Introductionmentioning

confidence: 99%

Cu-Based Catalysts Supported on H₃PO₄-Activated Coffee Biochar for Selective Reduction of Nitroaromatics

Gong,

Zhang,

et al. 2023

Langmuir

View full text Add to dashboard Cite

Selective reduction of nitroaromatics to the corresponding aromatic amines is extremely an attractive chemical process for both fundamental research and potential commercial applications. Herewith, we report that a highly dispersed Cu catalyst supported on H3PO4-activated coffee biochar and the resulting Cu/PBCR-600 catalyst show complete conversion of the nitroaromatics and >97.0% selectivity for the corresponding aromatic amines. The TOF of catalyzing the reduction of nitroaromatics (1.55–460.74 min–1) is approximately 2 to 15 times higher than those of previously reported non-noble and even noble metal catalysts. Additionally, Cu/PBCR-600 also shows high stability in catalytic recycles. Furthermore, it exhibits long-term catalytic stability (660 min) for practical application in a continuous-flow reactor. The characterizations and activity tests reveal that Cu0 existing in Cu/PBCR-600 acts as an active site in nitroaromatics reduction. Also, the further characterization by FTIR and UV–vis demonstrates that N, P co-doped coffee biochar could selectively adsorb and activate the nitro group of nitroaromatics.

show abstract

“…Metal–organic frameworks (MOFs) are ideal sacrificial precursors that can be used to construct a diverse range of structurally stable functional materials. 43–62 In this particular study, a bimetallic Ce/Zr MOF ( i.e. , CeZr-NH 2 -MOF) was synthesized via a liquid phase method by introducing a Ce source into the NH 2 -UiO-66 synthesis liquid.…”

Section: Introductionmentioning

confidence: 99%

Enhancing the efficiency of benzylamine oxidative coupling over N-doped porous carbon-supported CeO₂ and ZrO₂ nanoparticles

Chen,

Jian,

Zhuang

et al. 2023

New J. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

Construction of isolated Ni sites on nitrogen-doped hollow carbon spheres with Ni–N3 configuration for enhanced reduction of nitroarenes

Cited by 21 publications

References 70 publications

Mechanism of Catalytic Transfer Hydrogenation for Furfural Using Single Ni Atom Catalysts Anchored to Nitrogen-Doped Graphene Sheets

Mechanism of Catalytic Transfer Hydrogenation for Furfural Using Single Ni Atom Catalysts Anchored to Nitrogen-Doped Graphene Sheets

Cu-Based Catalysts Supported on H₃PO₄-Activated Coffee Biochar for Selective Reduction of Nitroaromatics

Enhancing the efficiency of benzylamine oxidative coupling over N-doped porous carbon-supported CeO₂ and ZrO₂ nanoparticles

Contact Info

Product

Resources

About

Construction of isolated Ni sites on nitrogen-doped hollow carbon spheres with Ni–N3 configuration for enhanced reduction of nitroarenes

Cited by 21 publications

References 70 publications

Mechanism of Catalytic Transfer Hydrogenation for Furfural Using Single Ni Atom Catalysts Anchored to Nitrogen-Doped Graphene Sheets

Mechanism of Catalytic Transfer Hydrogenation for Furfural Using Single Ni Atom Catalysts Anchored to Nitrogen-Doped Graphene Sheets

Cu-Based Catalysts Supported on H3PO4-Activated Coffee Biochar for Selective Reduction of Nitroaromatics

Enhancing the efficiency of benzylamine oxidative coupling over N-doped porous carbon-supported CeO2 and ZrO2 nanoparticles

Contact Info

Product

Resources

About

Cu-Based Catalysts Supported on H₃PO₄-Activated Coffee Biochar for Selective Reduction of Nitroaromatics

Enhancing the efficiency of benzylamine oxidative coupling over N-doped porous carbon-supported CeO₂ and ZrO₂ nanoparticles