Factors controlling oxophilicity and carbophilicity of transition metals and main group metals

Kayode, Gbolade O.; Montemore, Matthew M.

doi:10.1039/d1ta06453c

Cited by 34 publications

(25 citation statements)

References 47 publications

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“…Among the traditional transition metal elements, Fe and Co atoms exhibit relatively positive values (−1.86 and −1.93) of the d-band center, which means that they could have a strong interaction with the adsorbate nitrogen molecules (Supporting Information, Figure S30b). − The similar property also occurs in the spinel iron cobalt oxide in Figure a. The values of the d-band center of Fe(II) and Co(III) atoms are −1.46 and −1.68 eV, respectively, which indicates that the low oxidation state of iron could exhibit a better nitrogen adsorption property .…”

Section: Resultssupporting

confidence: 56%

“…When chemical adsorption occurs on the surface of transition metal surfaces, the d-band of the transition metal and the orbital of adsorbates combine, resulting in a bonded and an antibonded state, according to d-band center theory (Supporting Information, Figure S30a). As a result, the transition metal displays a stronger chemical bonding of absorbate molecules. Among the traditional transition metal elements, Fe and Co atoms exhibit relatively positive values (−1.86 and −1.93) of the d-band center, which means that they could have a strong interaction with the adsorbate nitrogen molecules (Supporting Information, Figure S30b).…”

Section: Resultsmentioning

confidence: 99%

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Boosting Photocatalytic Nitrogen Fixation via Constructing Low-Oxidation-State Active Sites in the Nanoconfined Spinel Iron Cobalt Oxide

Xia

Chong

et al. 2022

ACS Catal.

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The achievement of both N2 enrichment and activation of NN bonds on active sites in the photocatalytic nitrogen reduction reaction (NRR) under environmental conditions is a long-sought-after goal. Here, a nanoconfined spinel iron cobalt oxide (FeCo2O4) is prepared, which has a low oxidation state and stronger Fe’s 3d orbital electron-donating capability of iron active sites and can efficiently transfer electrons to N2 π* orbitals to facilitate activation of nitrogen. Additionally, we rationally control the mass transfer of nitrogen molecules in a nanoconfined interior cavity via the nanoconfined effect, forcing the N2 enrichment in the iron cobalt oxide semiconductor. In this work, the NRR performance of the nanoconfined iron cobalt oxide photocatalyst achieves 1.26 μmol h–1 (10 mg of photocatalyst addition), which is 3.7 times higher than that of bulk FeCo2O4. Our proposed strategy simultaneously satisfies both N2 capture and activation of nitrogen and instructs the development of low-oxidation-state iron-based photocatalysts for nitrogen fixation.

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Section: Resultssupporting

confidence: 56%

Section: Resultsmentioning

confidence: 99%

Boosting Photocatalytic Nitrogen Fixation via Constructing Low-Oxidation-State Active Sites in the Nanoconfined Spinel Iron Cobalt Oxide

Xia

Chong

et al. 2022

ACS Catal.

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“…Further tuning of the Cu-Zn NCs (e.g., changing the relative domain size) might increase further the FE toward this product. Based on its non-negligible propensity to generate CO from CO 2 and intrinsic elemental properties, , Ga sites in Cu might behave similarly; thus, studies on CuGa NCs are worthy to pursue.…”

Section: Directing Co2rr Selectivity By Structural and Compositional ...mentioning

confidence: 99%

Well-Defined Copper-Based Nanocatalysts for Selective Electrochemical Reduction of CO₂ to C₂ Products

2022

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The electrochemical CO2 reduction reaction (CO2RR) holds the promise to revolutionize the chemical industry by producing value-added chemicals and fuels from CO2 and water while storing renewable energy. However, catalyst design still remains one of the major hurdles in the field. This Perspective discusses the current and future contributions of well-defined nanocatalysts to improving the CO2RR selectivity toward C2 products, particularly ethylene and ethanol. In this regard, the shape and size selectivity dependence of single metal copper nanocrystals is briefly reviewed and linked to single-crystal studies. Representative studies on Cu-based bimetallic nanocrystals are discussed to highlight the importance of composition and distribution of the metals for selectivity. Finally, a vision on design strategies in terms of shape and composition for the next generation of CO2RR nanocatalysts is proposed.

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“…63 For example, oxygen-free Ti defect sites has been proposed as active sites for preferential adsorption of C=O bond in cinnamaldehyde. [64][65][66][67] DFT calculation shows crotonaldehyde adsorption energies on Ti1/Cu(111) is -2. Preliminary studies show that Ti doping of npCu significantly enhances the activity for both crotonaldehyde and butyraldehyde hydrogenation (Figure 6).…”

Section: Selective Hydrogenation Studiesmentioning

confidence: 99%

Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti-Cu Catalysts

Lee

Foucher

et al. 2022

Preprint

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The dissociation of H2 is an essential elementary step in many industrial chemical transformations, typically requiring precious metals. Here, we report a hierarchical nanoporous Cu catalyst doped with small amounts of Ti (npTiCu) that increases the rate of H2-D2 exchange by approximately one order of magnitude compared to the undoped nanoporous Cu (npCu) catalyst. The promotional effect of Ti was measured via steady-state H2-D2 exchange reaction experiments under atmospheric pressure flow conditions in the temperature range of 300─523 K. Pretreatment with flowing H2 is required for stable catalytic performance and two temperatures, 523 K and 673 K, were investigated. The experimentally-determined H2-D2 exchange rate is 5-7 times greater for npTiCu vs. the undoped Cu material under optimized pretreatment and reaction temperatures. The H2 pretreatment leads to full reduction of Cu oxide and partial reduction of surface Ti oxide species present in the as-prepared catalyst as demonstrated using in-situ ambient pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. The apparent activation energy and pre-exponential factors measured for H2-D2 exchange are substantially different for Ti-doped vs. undoped npCu catalysts. DFT calculations suggest that isolated, metallic Ti atoms on the surface of the Cu host can act as the active surface sites for hydrogen recombination. The increase in the rate of exchange above that of pure Cu is caused primarily by a shift in the rate-determining step from dissociative adsorption on Cu to H/D atom recombination on Ti-doped Cu, with the corresponding decrease in activation entropy that it produces.

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Factors controlling oxophilicity and carbophilicity of transition metals and main group metals

Abstract: The strength of interaction between a metal and oxygen and/or carbon is a crucial factor for catalytic performance, materials stability, and other important applications. While these are fundamental properties in...

Cited by 34 publications

References 47 publications

Boosting Photocatalytic Nitrogen Fixation via Constructing Low-Oxidation-State Active Sites in the Nanoconfined Spinel Iron Cobalt Oxide

Boosting Photocatalytic Nitrogen Fixation via Constructing Low-Oxidation-State Active Sites in the Nanoconfined Spinel Iron Cobalt Oxide

Well-Defined Copper-Based Nanocatalysts for Selective Electrochemical Reduction of CO₂ to C₂ Products

Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti-Cu Catalysts

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Factors controlling oxophilicity and carbophilicity of transition metals and main group metals

Abstract: The strength of interaction between a metal and oxygen and/or carbon is a crucial factor for catalytic performance, materials stability, and other important applications. While these are fundamental properties in...

Cited by 34 publications

References 47 publications

Boosting Photocatalytic Nitrogen Fixation via Constructing Low-Oxidation-State Active Sites in the Nanoconfined Spinel Iron Cobalt Oxide

Boosting Photocatalytic Nitrogen Fixation via Constructing Low-Oxidation-State Active Sites in the Nanoconfined Spinel Iron Cobalt Oxide

Well-Defined Copper-Based Nanocatalysts for Selective Electrochemical Reduction of CO2 to C2 Products

Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti-Cu Catalysts

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Product

Resources

About

Well-Defined Copper-Based Nanocatalysts for Selective Electrochemical Reduction of CO₂ to C₂ Products