Transition-Metal Single Atoms in a Graphene Shell as Active Centers for Highly Efficient Artificial Photosynthesis

Jiang, Kun; Siahrostami, Samira; Akey, Austin; Li, Yanbin; Lu, Zhiyi; Lattimer, Judith; Hu, Yongfeng; Stokes, Chris R.; Gangishetty, Mahesh K.; Chen, Guangxu; Zhou, Yawei; Hill, Winfield; Cai, Wen; Bell, David C.; Chan, Karen; Nørskov, Jens K.; Cui, Yi; Wang, Haotian

doi:10.1016/j.chempr.2017.09.014

Cited by 363 publications

(333 citation statements)

References 58 publications

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“…Density functional theory (DFT) calculations were performed to gain insight into the activity and selectivity of Co‐NC and Ni‐NC catalysts for HER and CO 2 RR. The binding energy of key reaction intermediates *H (for HER), and *HOCO and *CO (for CO 2 RR) were calculated on Co‐N 4 and Ni‐N 4 centers embedded in a 4×4 graphene supercell (Figure a), which have been proposed as potential active sites of Co‐NC and Ni‐NC catalysts, respectively . Figures a–f show the optimized structures of unit cells used in DFT calculations and the energetically most favorable adsorption configurations of the intermediates *H, *CO, and *HOCO on TM‐N 4 (TM=Co, Ni) centers.…”

Section: Figurementioning

confidence: 99%

Electrochemical Conversion of CO₂ to Syngas with Controllable CO/H₂ Ratios over Co and Ni Single‐Atom Catalysts

et al. 2020

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The electrochemical CO2 reduction reaction (CO2RR) to yield synthesis gas (syngas, CO and H2) has been considered as a promising method to realize the net reduction in CO2 emission. However, it is challenging to balance the CO2RR activity and the CO/H2 ratio. To address this issue, nitrogen‐doped carbon supported single‐atom catalysts are designed as electrocatalysts to produce syngas from CO2RR. While Co and Ni single‐atom catalysts are selective in producing H2 and CO, respectively, electrocatalysts containing both Co and Ni show a high syngas evolution (total current >74 mA cm−2) with CO/H2 ratios (0.23–2.26) that are suitable for typical downstream thermochemical reactions. Density functional theory calculations provide insights into the key intermediates on Co and Ni single‐atom configurations for the H2 and CO evolution. The results present a useful case on how non‐precious transition metal species can maintain high CO2RR activity with tunable CO/H2 ratios.

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Section: Figurementioning

confidence: 99%

Electrochemical Conversion of CO₂ to Syngas with Controllable CO/H₂ Ratios over Co and Ni Single‐Atom Catalysts

et al. 2020

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“…Some M-N-C (porphyrin)-contained SACs have been synthesized for electrocatalytic applications. In general, CO 2 RR pathways can be divided into four elementary steps, including: [22] (i) CO 2 adsorption, (ii) CO 2 activation, Adv. In general, CO 2 RR pathways can be divided into four elementary steps, including: [22] (i) CO 2 adsorption, (ii) CO 2 activation, Adv.…”

Section: Reaction Pathways and Scaling Relationshipmentioning

confidence: 99%

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion

Gong

Zhang

Lin

et al. 2019

Advanced Energy Materials

192

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energy such as wind and solar energy has attracted enormous interest for its significant roles in mitigating CO 2 emissions and reducing dependence on petrochemicals. [1,2] At the heart of the CO 2 conversion technology, electrocatalysts are needed to promote a critical reaction, CO 2 reduction reaction (CO 2 RR) that determines the efficiency and selectivity. To date, the electrocatalysts have confronted severe bottlenecks issue: poor selectivity about various accessory products in CO 2 conversion process, and loss of efficiency toward competing hydrogen evolution. [3] The former involves associated multielectron transfer process and is difficult to accurately control the reaction process by external conditions, [4] while the latter is mainly due to the fact that the equilibrium potentials for most of the CO 2 RR are very close to hydrogen evolution reaction (HER) toward undesirable side-products in aqueous electrolytes, which degrades the electrocatalytic performance during the CO 2 RR process. [5,6] Therefore, CO 2 RR is much more complex than other energy-related electrochemical reactions such as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and it is still a great challenge to design and synthesize electrocatalytic materials with higher product selectivity and catalytic activity for CO 2 RR.Among the electrocatalysts including metals oxides and metal-doped carbon materials, single-atom catalysts (SACs) represent an exciting class of catalysts with monodispersed metal catalytic centers and have emerged as the frontier science in both homogeneous and heterogeneous catalysis, including CO 2 conversion. [7][8][9][10] This type of catalysts contains M-N-C moiety with single atoms and is common in building metalorganic frameworks (MOFs), [11] covalent organic frameworks (COFs) [12] with transition metal macrocyclic clusters, such as porphyrin, phthalocyanine, and tetraazannulene, as well as metal-doped carbon materials [13] (e.g., graphene, carbon nanotubes, fullerene). In nature, the biomolecules, like chlorophyll (Mg-porphyrin) in leaves, and iron porphyrins in cytochrome c oxidase in blood cells, have similar structures as SACs, with special ability in photosynthesis and transforming CO 2 from cells with high efficiency and selectivity. [14] Through the selection of appropriate motifs, the construction principles of Direct conversion of CO 2 into carbon-neutral fuels or industrial chemicals holds a great promise for renewable energy storage and mitigation of greenhouse gas emission. However, experimentally finding an electrocatalyst for specific final products with high efficiency and high selectivity poses serious challenges due to multiple electron transfer, complicated intermediates, and numerous reaction pathways in electrocatalytic CO 2 reduction. Here, an intrinsic descriptor that correlates the catalytic activity with the topological, bonding, and electronic structures of catalytic centers on M-N-C based single-atom catalysts is discovered. The "volcano"-shaped relationships betwee...

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“…In addition, the electrospinning method was also employed to construct the electrocatalyst of single Ni atom coordinated with N atoms, bearing similar high CRR activity with the NiN/G catalyst. As a typical example, using polyacrylonitrile, polypyrrolidone, Ni(NO 3 ) 2 , dicyandiamide, and dimethylformamide as precursors, the Ni‐based graphene shells' catalyst (denoted as NiN‐GS) was electrospun into nanofibers by the oxidation and carbonization processes . In the unique structure, the partial Ni atoms that are mostly coordinated with C atoms but less coordinated with N atoms were dispersed on the carbon as single atoms distinguished from Ni NPs.…”

Section: Carbon‐rich Npmsacs For Crr and Hermentioning

confidence: 99%

Carbon‐Rich Nonprecious Metal Single Atom Electrocatalysts for CO₂ Reduction and Hydrogen Evolution

et al. 2019

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Single atom catalysts (SACs) are considered as the emerging catalysts for boosting electricity‐driven CO2 reduction reaction (CRR) and hydrogen evolution reaction (HER). To replace the rare and expensive noble metal electrocatalysts, developing nonprecious metal SACs (NPMSACs) with superior electrocatalytic activity and stability is of paramount importance for achieving high efficiency in CRR and HER. Herein, a brief overview of recent achievements in the carbon‐rich NPMSACs for both CRR and HER is provided. The synthesis strategies and corresponding electrocatalytic performances of various carbon‐rich NPMSACs are discussed in the order of various metals (Ni, Co, Fe, Zn, and Sn for CRR, as well as Ni, Co, Fe, Mo, and W for HER), with a special attention paid to understand the structure–activity relationships. Finally, the remaining challenges and future perspectives for enhancing CRR and HER performance of NPMSACs are outlined.

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Transition-Metal Single Atoms in a Graphene Shell as Active Centers for Highly Efficient Artificial Photosynthesis

Cited by 363 publications

References 58 publications

Electrochemical Conversion of CO₂ to Syngas with Controllable CO/H₂ Ratios over Co and Ni Single‐Atom Catalysts

Electrochemical Conversion of CO₂ to Syngas with Controllable CO/H₂ Ratios over Co and Ni Single‐Atom Catalysts

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion

Carbon‐Rich Nonprecious Metal Single Atom Electrocatalysts for CO₂ Reduction and Hydrogen Evolution

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Transition-Metal Single Atoms in a Graphene Shell as Active Centers for Highly Efficient Artificial Photosynthesis

Cited by 363 publications

References 58 publications

Electrochemical Conversion of CO2 to Syngas with Controllable CO/H2 Ratios over Co and Ni Single‐Atom Catalysts

Electrochemical Conversion of CO2 to Syngas with Controllable CO/H2 Ratios over Co and Ni Single‐Atom Catalysts

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO2 Conversion

Carbon‐Rich Nonprecious Metal Single Atom Electrocatalysts for CO2 Reduction and Hydrogen Evolution

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Electrochemical Conversion of CO₂ to Syngas with Controllable CO/H₂ Ratios over Co and Ni Single‐Atom Catalysts

Electrochemical Conversion of CO₂ to Syngas with Controllable CO/H₂ Ratios over Co and Ni Single‐Atom Catalysts

Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO₂ Conversion

Carbon‐Rich Nonprecious Metal Single Atom Electrocatalysts for CO₂ Reduction and Hydrogen Evolution