π-Adsorption promoted electrocatalytic acetylene semihydrogenation on single-atom Ni dispersed N-doped carbon

Ma, Wenxiu; Chen, Zhe; Bu, Jun; Liu, Zhenpeng; Li, Jinjin; Chen, Yan; Cheng, Lin; Zhang, Lei; Zhang, Hepeng; Zhang, Jichao; Wang, Tao; Zhang, Jian

doi:10.1039/d1ta08002d

Cited by 31 publications

(13 citation statements)

References 43 publications

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“…In addition, isolating the active sites was also shown to be beneficial for improving the selectivity to ethylene as that demonstrated in thermocatalytic hydrogenation. Fabricating a single-atom Ni catalyst featuring isolated sites was reported for electrocatalytic acetylene semihydrogenation . The π-adsorption configuration for ethylene endowed by the isolated Ni sites favored the desorption process over the hydrogenation to ethane, and thus enhanced the selectivity.…”

Section: Photo-/electrocatalytic Semihydrogenationmentioning

confidence: 99%

“…Fabricating a single-atom Ni catalyst featuring isolated sites was reported for electrocatalytic acetylene semihydrogenation. 183 The π-adsorption configuration for ethylene endowed by the isolated Ni sites favored the desorption process over the hydrogenation to ethane, and thus enhanced the selectivity. Notably, the photo/electrocatalytic semihydrogenation processes proceed without feeding H 2 , normally employing water as the source of hydrogen.…”

Section: Photo-/electrocatalytic Semihydrogenationmentioning

confidence: 99%

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Mechanistic and Atomic-Level Insights into Semihydrogenation Catalysis to Light Olefins

Yan

Cao

et al. 2022

ACS Catal.

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Semihydrogenations of alkynes and alkadienes to light olefins catalyzed by a heterogeneous catalyst are widely applied in the chemical industry, but it remains challenging to design high-performance catalysts for these processes. The well-developed synthesis methodologies, characterization techniques for catalyst structures, and theoretical calculations in recent decades render opportunities for understanding mechanisms and elaborating the structures of active sites at the atomic level. This Review summarizes recent advances in the mechanistic and atomic-level insights into semihydrogenation catalysis for alkynes and alkadienes to light olefins. The structure-sensitivity, information on active sites, and reaction kinetics are initially discussed to demonstrate the knowledge on the mechanistic and kinetics details of the hydrogenations of alkynes and alkadienes. We then introduce the regulations for the active sites, especially at the atomic level, based on three categories, i.e., site-isolation, local environment regulation, and oxygen vacancy and interfacial sites. Followed by the discussion on the conventional thermocatalytic hydrogenations, the emerging photocatalytic and electrocatalytic semihydrogenations of alkynes and alkadienes are further covered. Finally, we provide a brief overview on the current status of this field and a perspective for future study on the atomic-level design and regulation of catalysts for controlling the selectivity to target products.

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Section: Photo-/electrocatalytic Semihydrogenationmentioning

confidence: 99%

Section: Photo-/electrocatalytic Semihydrogenationmentioning

confidence: 99%

Mechanistic and Atomic-Level Insights into Semihydrogenation Catalysis to Light Olefins

Yan

Cao

et al. 2022

ACS Catal.

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“…44 Nowadays, 3d-metal-based single atomic catalysts (SAC) are becoming a promising candidate for developing more efficient catalytic systems for various organic transformations because of their improved atom-utilization efficiency. [45][46][47][48][49][50][51][52] Moreover, the unique electronic structure of the single metal centre on the surface and labile coordination environment around the active site play a vital role in its unique catalytic activity compared to their nanoparticle or nanocluster counterparts. 53,54 Recently, several cobalt-based SACs were developed for hydrogenation/dehydrogenation related chemistry, which showed excellent catalytic activities in diverse range of organic transformations.…”

Section: Introductionmentioning

confidence: 99%

In-depth experimental and theoretical investigations on Co-SAC catalyzed transfer hydrogenation of azo compounds using methanol and ethanol

Panja

Mahapatra

Dey

et al. 2023

Preprint

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Transfer hydrogenation of non-polar bond using methanol or ethanol such hydrogen source is of great challenge, and development of efficient catalyst for performing such challenging reactions always an exciting area to explore. Herein, using Co-SAC various azo bonds were very efficiently hydrogenated to the corresponding amines, including commercially used dyes. A number of kinetics study and Hammett studies were to investigate the plausible mechanism and electronic effects. Further, a detailed DFT-calculation was performed to get a deeper insight about the mechanism.

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“…As a result, Cu 3 (HITP) 2 with the smallest ∆ε (0.10 eV) exhibits the highest TOF of 0.36 s −1 , which outperforms those of previously reported electrocatalysts. [4,14,15,27] Meanwhile, the ethylene partial current density (j C2H4 ) and Faradaic efficiency (FE) of Cu 3 (HITP) 2 markedly reach −124 mA cm −2 and 99.3% at −0.9 V versus RHE, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…[14] Subsequently, the electrocatalysts featuring weak π-adsorption of acetylene, e.g., our recent work on single-metalsite catalysts and Ag nanowires, which prevents the occurrence of side reactions acetylene C-C coupling. [15,16] Nevertheless, such electrocatalysts show low intrinsic activity like turnover frequencies (TOFs) (<0.12 s −1 ). Therefore, to correlate the structure of metal sites and electrocatalytic activity of alkyne semihydrogenation is urgently necessary for guiding the exploration of high-performance electrocatalysts, but remains elusive.…”

mentioning

confidence: 99%

Pairing d‐Band Center of Metal Sites with π‐Orbital of Alkynes for Efficient Electrocatalytic Alkyne Semi‐Hydrogenation

Guo

Chang

et al. 2022

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Electrocatalytic alkyne semi‐hydrogenation has attracted ever‐growing attention as a promising alternative to traditional thermocatalytic hydrogenation. However, the correlation between the structure of active sites and electrocatalytic performance still remains elusive. Herein, the energy difference (∆ε) between the d‐band center of metal sites and π orbital of alkynes as a key descriptor for correlating the intrinsic electrocatalytic activity is reported. With two‐dimensional conductive metal organic frameworks as the model electrocatalysts, theoretical and experimental investigations reveal that the decreased ∆ε induces the strengthened d–π orbitals interaction, which thus enhances acetylene π‐adsorption and accelerates subsequent hydrogenation kinetics. As a result, Cu3(HITP)2 featuring the smallest ∆ε (0.10 eV) delivers the highest turnover frequency of 0.36 s−1, which is about 124 times higher than 2.9 × 10−3 s−1 for Co3(HITP)2 with the largest ∆ε of 2.71 eV. Meanwhile, Cu3(HITP)2 presents a high ethylene partial current density of −124 mA cm−2 and a large ethylene Faradaic efficiency of 99.3% at −0.9 V versus RHE. This work will spark the rapid exploration of high‐activity alkyne semi‐hydrogenation catalysts.

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π-Adsorption promoted electrocatalytic acetylene semihydrogenation on single-atom Ni dispersed N-doped carbon

Abstract: As a novel electrocatalyst for acetylene semihydrogenation, single-atom nickel dispersed N-doped carbon exhibits a high acetylene conversion of 97.4%, which are attributed to weak π-adsorption of ethylene on individual Ni sites.

Cited by 31 publications

References 43 publications

Mechanistic and Atomic-Level Insights into Semihydrogenation Catalysis to Light Olefins

Mechanistic and Atomic-Level Insights into Semihydrogenation Catalysis to Light Olefins

In-depth experimental and theoretical investigations on Co-SAC catalyzed transfer hydrogenation of azo compounds using methanol and ethanol

Pairing d‐Band Center of Metal Sites with π‐Orbital of Alkynes for Efficient Electrocatalytic Alkyne Semi‐Hydrogenation

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