Active site engineering of atomically dispersed transition metal-heteroatom-carbon catalysts for oxygen reduction

2021 ◽  
Author(s):  
Jiawei Zhu ◽  
Shichun Mu
Keyword(s):  
Transition Metal ◽  
Oxygen Reduction ◽  
Active Site ◽  
Catalytic Reactions ◽  
Single Atom ◽  
Carbon Catalysts

Owing to the advantage of atomic utilization, the single-atom catalyst has attracted much attention and been employed in multifarious catalytic reactions. Their definite site configuration is favorable for exploring the...

Recent Advances in Phosphorus‐Coordinated Transition Metal Single‐Atom Catalysts for Oxygen Reduction Reaction

ChemNanoMat ◽  
2020 ◽  
Vol 6 (11) ◽  
pp. 1601-1610
Author(s):  
Fengzhi Ning ◽  
Xin Wan ◽  
Xiaofang Liu ◽  
Ronghai Yu ◽  
Jianglan Shui
Keyword(s):  
Transition Metal ◽  
Oxygen Reduction Reaction ◽  
Oxygen Reduction ◽  
Reduction Reaction ◽  
Single Atom ◽  
Recent Advances

scholarly journals Unified Mechanistic Understanding of CO2 Reduction to CO on Transition Metal and Single Atom Catalysts

2021 ◽  
Author(s):  
Sudarshan Vijay ◽  
Wen Ju ◽  
Sven Brückner ◽  
Peter Strasser ◽  
Karen Chan
Keyword(s):  
Electron Transfer ◽  
Electronic Structure ◽  
Transition Metal ◽  
Density Functional ◽  
Co2 Reduction ◽  
Electron Transfer Reaction ◽  
Dipole Field ◽  
Single Atom ◽  
Activity Measurements ◽  
Carbon Catalysts

<p>CO is the simplest product from CO<sub>2</sub> electroreduction (CO<sub>2</sub>R), but the identity and nature of its rate limiting step remains controversial. Here we investigate the activity of both transition metals (TMs) and metal-nitrogen doped carbon catalysts (MNCs), and a present unified mechanistic picture of CO<sub>2</sub>R to for both these classes of catalysts. By consideration of the electronic structure through a Newns-Andersen model, we find that on MNCs, like TMs, electron transfer to CO<sub>2</sub><sub> </sub>is facile, such that CO<sub>2</sub> (g) adsorption is driven by adsorbate dipole-field interactions. Using density functional theory with explicit consideration of the interfacial field, we find CO<sub>2</sub> * adsorption to generally be limiting on TMs, while MNCs can be limited by either CO<sub>2</sub>* adsorption or by the proton-electron transfer reaction to form COOH*. We evaluate these computed mechanisms against pH-dependent experimental activity measurements on CO<sub>2</sub>R to CO activity for Au, FeNC, and NiNC. We present a unified activity volcano that, in contrast to previous analyses, includes the decisive CO<sub>2</sub>*<sub> </sub>and COOH* binding strengths as well as the critical adsorbate dipole-field interactions. We furthermore show that MNC catalysts are tunable towards higher activity away from transition metal scaling, due to the stabilization of larger dipoles resulting from their discrete and narrow <i>d</i>-states. The analysis suggests two design principles for ideal catalysts: moderate CO<sub>2</sub>* and COOH* binding strengths as well as large dipoles on the CO<sub>2</sub>*<sub> </sub>intermediate. We suggest that these principles can be exploited in materials with similar electronic structure to MNCs, such as supported single-atom catalysts, molecules, and nanoclusters, 2D materials, and ionic compounds towards higher CO<sub>2</sub>R activity. This work captures the decisive impact of adsorbate dipole-field interactions in CO<sub>2</sub>R to CO and paves the way for computational-guided design of new catalysts for this reaction.</p>

Transition metal templates as guides for cyclizations

1988 ◽  
Vol 326 (1592) ◽  
pp. 511-524 ◽  
Keyword(s):  
Transition Metal ◽  
Active Site ◽  
Alder Reaction ◽  
Diels Alder ◽  
Catalytic Reactions ◽  
Cyclization Reactions ◽  
The Third ◽  
Organic Systems ◽  
Diels Alder Reaction ◽  
Macrocyclic Ethers

The improvement of synthetic efficiency requires the development of more chemo-, regio-, diastereo- and enantioselective methods. Transition metal templates form the equivalent of an ‘active site’ to impose selectivity upon reacting organic systems. Such effects will be examined within the context of cyclization reactions. The first part examines cyclization reactions invoking intramolecular carbametallation. Catalytic reactions involving at least three different mechanisms and two different metals provide five- and six-membered rings from enynes and diynes. A second strategy invokes transition metal templates to facilitate macrocyclization. Formation of macrocarbocycles, macrolactones and macrocyclic ethers and amines illustrates the versatility of this approach. Most importantly, many of the macrocyclizations proceed at normal concentrations of 0.25-0.50 m . The third strategy invokes cycloadditions. A transition metal equivalent to the Diels-Alder reaction permits formation of odd membered rings by [2« + 3] cycloadditions for n = 1, 2 and 3. The applicability that such methods have in devising new synthetic strategies towards biologically important natural products will be illustrated.

scholarly journals Highly selective oxygen reduction to hydrogen peroxide on transition metal single atom coordination

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Kun Jiang ◽  
Seoin Back ◽  
Austin J. Akey ◽  
Chuan Xia ◽  
Yongfeng Hu ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Transition Metal ◽  
Oxygen Reduction ◽  
Single Atom

Transition Metal-Nitrogen-Carbon Active Site for Oxygen Reduction Electrocatalysis: Beyond the Fascinations of TM-N4

ChemCatChem ◽  
2018 ◽  
Vol 11 (2) ◽  
pp. 655-668 ◽  
Author(s):  
Cai Zhang ◽  
Wei Zhang ◽  
Weitao Zheng
Keyword(s):  
Transition Metal ◽  
Oxygen Reduction ◽  
Active Site

Computational screening of efficient graphene-supported transition metal single atom catalysts toward the oxygen reduction reaction

2020 ◽  
Vol 8 (37) ◽  
pp. 19319-19327 ◽  
Author(s):  
Lei Li ◽  
Rao Huang ◽  
Xinrui Cao ◽  
Yuhua Wen
Keyword(s):  
Transition Metal ◽  
Oxygen Reduction Reaction ◽  
Oxygen Reduction ◽  
Reduction Reaction ◽  
Single Atom ◽  
Nitrogen Doped ◽  
Single Atoms ◽  
Computational Screening ◽  
Nitrogen Doped Graphene ◽  
Doped Graphene

Transition metal single atoms anchored on nitrogen-doped graphene toward the oxygen reduction reaction have been screened.

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