Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon

Genovese, Chiara; Schuster, Manfred Erwin; Gibson, Emma K.; Gianolio, Diego; Posligua, Víctor; Grau‐Crespo, Ricardo; Cibin, Giannantonio; Wells, Peter P.; Garai, Debi; Solokha, Vladyslav; Calderón, Sandra Krick; Velasco-Vélez, Juan-Jesús; Ampelli, Claudio; Perathoner, Siglinda; Held, Georg; Arrigo, Rosa

doi:10.1038/s41467-018-03138-7

Cited by 194 publications

(207 citation statements)

References 49 publications

(62 reference statements)

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“…With the development of advanced instruments and characterization techniques, researchers are able to gain deeper insight into the structure of single atoms in the SACs, including its chemical environment and spatial structure. In this section, we would review the specific technologies for analyzing the structure of SACs.…”

Section: Fabrication Of Densely Populated Sacsmentioning

confidence: 99%

Densely Populated Single Atom Catalysts

et al. 2019

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Developing highly efficient electrocatalysts with low cost is critical for the wide‐spread application of sustainable and renewable energy conversion technologies. Single‐atom catalysts (SACs) have attracted considerable attention owing to their high catalytic activity, selectivity, and stability. However, the high surface energy of the single atoms often results in an extremely low loading of metal atom catalysts with limited mass activity. In this context, densely populated SACs are more promising for practical applications due to their high active surface area and mass activity. Herein, the recent research progress of high loading (≥5 wt%) SACs for different electrocatalytic applications is summarized. An overview of various synthesis and characterization strategies of SACs is presented in this review. The influence of appropriate substrates on the preparation of high metal loading SACs is also discussed. In addition, this review provides valuable insights into the current challenges and future opportunities in the field of single‐atom catalysts.

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Section: Fabrication Of Densely Populated Sacsmentioning

confidence: 99%

Densely Populated Single Atom Catalysts

et al. 2019

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“…Moreover, a systematic investigation by Huan et al into Fe SACs revealed that by tuning ratio of isolated Fe–N 4 sites compared to Fe nanoparticles, the CO:H 2 ratio can be tuned . The importance of Fe‐N coordination was further revealed by Genovese et al who utilized operando XAS and DFT to confirm the role of nitrogen‐coordinated Fe (II) single atom sites as responsible for the conversion of CO 2 to acetic acid at extremely low applied potential of −0.5 V versus Ag/AgCl . Overall, Fe SACs can be shown to demonstrate CO 2 RR activity that is greater than that of Co SACs .…”

Section: Active Sites In Metal‐carbon Catalystsmentioning

confidence: 99%

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO₂ to Value‐Added Chemicals and Fuel

Daiyan

Saputera

Masood

et al. 2020

Advanced Energy Materials

122

104

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Renewable‐electricity‐powered electrocatalytic CO2 reduction reactions (CO2RR) have been identified as an emerging technology to address the issue of rising CO2 emissions in the atmosphere. While the CO2RR has been demonstrated to be technically feasible, further improvements in catalyst performance through active sites engineering are a prerequisite to accelerate its commercial feasibility for utilization in large CO2‐emitting industrial sources. Over the years, the improved understanding of the interaction of CO2 with the active sites has allowed superior catalyst design and subsequent attainment of prominent CO2RR activity in literature. This review tracks the evolution of the understanding of CO2RR active sites on different electrocatalysts such as metals, metal‐oxides, single atoms, metal‐carbon, and subsequently metal‐free carbon‐based catalysts. Despite the tremendous research efforts in the field, many scientific questions on the role of various active sites in governing CO2RR activity, selectivity, stability, and pathways are still unanswered. These gaps in knowledge are highlighted and a discussion is set forth on the merits of utilizing advanced in‐situ and operando characterization techniques and machine learning (ML). Using this technique, the underlying mechanisms can be discerned, and as a result new strategies for designing active sites may be uncovered. Finally, this review advocates an interdisciplinary approach to discover and design CO2RR active sites (rather than focusing merely on catalyst activity) in a bid to stimulate practical research for industrial application.

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“…Charge and spin can be carefully tuned in surface-confined metal-organic networks, at least in UHV, and we tackle here the issue whether this fundamental bottom-up approach can be extended beyond the surface science UHV environmental constraints. Recently, the reactivity of tetrapyrrole monolayers at surfaces has been investigated in situ at the solid/liquid interface under electrochemical conditions, mainly by STM methods [20,[132][133][134][135][136][137][138][139][140][141][142]. Very recently, instead, surface science spectroscopic approaches combining SFG and NAP-XPS methods allowed extension of the investigations of the ligand-macrocycle interaction up to the mbar pressure regime at room temperature, thus close to applicative relevant conditions [14,37,99,105,108].…”

Section: A Fundamental Approach Beyond Uhvmentioning

confidence: 99%

Tetrapyrroles at near-ambient pressure: porphyrins and phthalocyanines beyond the pressure gap

Vesselli

2020

J. Phys. Mater.

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Many complex mechanisms underlying the fascinating functionalities provided by tetrapyrrolic macrocycles in biochemistry have been already unraveled. Light harvesting, molecular transport, and catalytic conversion are some of the processes performed by tetrapyrrole-based centers embedded in protein pockets. The main function is determined by the single atom species that is caged in the macrocycle, while a finer tuning (band gap, chemical selectivity etc) is granted by the geometric and electronic structure of the tetrapyrrole, including its residues, and by the proximal and distal structures of the protein surroundings that exploit the molecular trans-effect and direct weak interactions, respectively. Hence, a scientific and technological challenge consists in the artificial replication of both structure and functionality of natural reaction centers in 2D ordered arrays at surfaces. Nano-architected 2D metalorganic frameworks can be indeed self-assembled under controlled conditions at supporting surfaces and, in the specific, porphyrin-and phthalocyaninebased systems have been widely investigated in ultra-high vacuum conditions by means of surface science approaches. Deep insight into the geometry, electronic structure, magnetic properties, ligand adsorption mechanisms, and light absorption has been obtained, with the strong experimental constraint of vacuum. Especially in the case of the interaction of tetrapyrroles with ligands, this limit represents a relevant gap with respect to both comparison with natural counterparts from the liquid environment and potential applicative views at both solid-liquid and solid-gas interfaces. Thus, a step forward in the direction of near-ambient pressure is strongly necessary, while maintaining the atomiclevel detail characterization accuracy. Nowadays this becomes feasible by exploiting state-of-the-art experimental techniques, in combination with computational simulations. This review focusses on the latest advances in this direction.

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Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon

Cited by 194 publications

References 49 publications

Densely Populated Single Atom Catalysts

Densely Populated Single Atom Catalysts

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO₂ to Value‐Added Chemicals and Fuel

Tetrapyrroles at near-ambient pressure: porphyrins and phthalocyanines beyond the pressure gap

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Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon

Cited by 194 publications

References 49 publications

Densely Populated Single Atom Catalysts

Densely Populated Single Atom Catalysts

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO2 to Value‐Added Chemicals and Fuel

Tetrapyrroles at near-ambient pressure: porphyrins and phthalocyanines beyond the pressure gap

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A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO₂ to Value‐Added Chemicals and Fuel