Faraday Discussions最新文献

Templated synthesis is an intriguing strategy for the length-controlled synthesis of oligomers. Traditionally, such reactions require stoichiometric amounts of the template with respect to the product. Recently we reported catalytic macrocyclic templates that promote oligomerization of a small molecule substrate with a remarkable degree of length control. Herein we present our efforts toward creating linear templates for catalytic length-controlled oligomer synthesis.

With the increase in the greenhouse effect and reduction of fossil fuel resources, it is urgent to find a feasible solution to directly convert power to chemicals using renewable energy and achieving zero carbon emissions targets. It is necessary to convert renewable energy (i.e., solar, wind, water, etc.) into electrical power replacing fossil-fuel-fired power. Therefore, the power-to-chemicals approach is gaining more and more attention. In the past two decades, non-thermal plasma, electro-catalysis, photo-catalysis, and their hybrid approaches have shown great potential for the power-to-chemicals solution. This paper introduces the application of plasma technology in energy conversion, focusing on three main routes for plasma-enabled ammonia synthesis, and analyses the state-of-the-art. Research results of ammonia synthesis based on plasma technology are discussed. The application of advanced in situ diagnostics evidences the importance of specific intermediate species and reaction pathways. Electrons, vibrationally-excited species, free radicals, and surface-adsorbed species play important roles in plasma-catalytic ammonia synthesis. Combined with experiments and simulations, the mechanisms of plasma-catalytic ammonia synthesis are examined. Vibrationally-excited species can effectively reduce the catalytic surface energy barrier. The techno-economics of the plasma-enabled ammonia synthesis technology is discussed in view of its competitive advantages. It is emphasized that the power-to-chemicals approach can be adapted for most chemical manufacturers, and these methods would play crucial roles in reducing carbon emissions and environmental pollution. Finally, suggestions are provided for the sustainable development of the power-to-chemicals industry in the future.

Photoredox catalysis is a valuable tool in a large variety of chemical reactions. Main challenges still to be overcome are photodegradation of photocatalysts and substrates, short lifetimes of reactive intermediates, and selectivity issues due to unwanted side reactions. A potential solution to these challenges is the pre-organization of the photosensitizer, substrate and (co)-catalyst in supramolecular self-assembled structures. In such architectures, (organic) dyes can be stabilized, and higher selectivity could potentially be achieved through pre-organizing desired reaction partners via non-covalent interactions. Perylene diimide (PDI) is an organic dye, which can be readily reduced to its mono- and dianion. Excitation of both anions leads to highly reducing excited states, which are able to reduce a variety of substrates via single electron transfer. The incorporation of PDI into a heteroleptic [M₄L^a₂L^b₂] supramolecular square has been recently demonstrated. Herein we investigate its photophysical properties and demonstrate that incorporated PDI indeed features photocatalytic activity. Initial results suggest that the pre-organisation by binding positively affects the outcome.

N₂ dissociative adsorption is commonly the rate-determining step in thermal ammonia synthesis. Herein, we performed density functional theory (DFT) calculations to understand the N₂ dissociation mechanism on models of unsupported Ru(0001) terraces, Ru B5 sites, and polar MgO(111)-supported Ru₈ cluster mimicking a B5 site geometry, denoted (Ru₈(B5-like)/MgO(111)). The activation energy of N₂ dissociative adsorption on the Ru₈(B5-like)/MgO(111) model (E_a = 0.33 eV) is much lower than that on the unsupported Ru(0001) terrace (E_a = 1.74 eV) and Ru B5 (E_a = 0.62 eV) models. The lower N₂ dissociation barrier on Ru B5 sites is facilitated by the enhanced σ donation and π* back-donation between N₂(σ, π*) and Ru(d) orbitals resulting in the stronger activation of the molecular side-on N₂* dissociation precursor. The Ru₈(B5-like)/MgO(111) also exhibits enhanced σ donation because of the B5-like cluster geometry. Furthermore, the Ru cluster of the bare Ru₈(B5-like)/MgO(111) model is positively charged. This induced an unusual π donation from N₂(π) to Ru(d) orbitals as revealed by analyses of the density of states and partial charge densities. The combined σ and π donation resulted in an increased synergistic π* back-donation. The total interactions between N₂(σ, π, π*) and Ru(d) resulted in an overall electron transfer to the adsorbed N₂ from the Ru atoms in the B5-like site with no direct involvement of the MgO(111) substrate. Analyses of bond stretching vibrations and bond lengths show that the N₂(σ, π, π*) and Ru(d) interactions lead to a weaker N–N bond and stronger Ru–N bonds. These correspond to a lower barrier of N₂ dissociation on the Ru₈(B5-like)/MgO(111) model, where the highest red-shift of N–N vibration and the longest N–N bond length were observed after side-on N₂* adsorption. These results demonstrate that an electron-deficient Ru catalyst are not always inhibited from donating electrons to adsorbed N₂. Rather, this study shows that the electron deficiency of Ru can promote π* back-donation and N₂ activation. These new insights may therefore open new avenues to design supported Ru catalysts for nitrogen activation.

Ruthenium–NHC based catalysts, with a chelated iminium ligand trans to the N-heterocyclic carbene (NHC) ligand, that polymerize dicyclopentadiene (DCPD) at different temperatures are monitored using Density Functional Theory calculations to unveil the reaction mechanism, and subsequently how important are the geometrical and electronic features vs. the non-covalent interactions in between. The balance is very fragile and H-bonds are fundamental to explain the different behaviour of latent catalysts. This computational study aims to facilitate future studies of new generations of latent initiators for olefin metathesis polymerization, with the 3D and mainly the 2D Non-Covalent Interaction plots the characterization tool for H-bonds.

Modulating the interaction between Mo nanoparticles and their support is an elegant approach to finely tune the structural, physico-chemical, redox and electronic properties of the active site. In this work, a series of molybdenum nitride catalysts supported on TiO₂, and SBA-15 has been prepared and fully characterized. The results of characterization confirmed the high dispersion of Mo and the formation of small molybdenum nanoparticles in both the 10-Mo-N/SBA-15 and 10-Mo-N/TiO₂ catalysts. In this context, we have shown that the catalytic activity of Mo species was strongly impacted by the nature of the catalytic support. Amongst the studied supports, SBA-15 was found to be the most appropriate for Mo dispersion. In comparison, when supported on a reducible oxide (TiO₂), Mo species showed poor catalytic activity in both ammonia synthesis and decomposition and were prone to quick deactivation in the ammonia synthesis reaction. Evidence of charge transfer from the reducible support to the active phase, indicative of possible SMSI behaviour, has been observed by XPS and EPR. Differences in the oxidation states, redox behaviours, and electronic properties have been further studied by means of EPR, H₂-TPR and H₂-TPD.

Study of α-V70I-substituted nitrogenase MoFe protein identified Fe6 of FeMo-cofactor (Fe₇S₉MoC-homocitrate) as a critical N₂ binding/reduction site. Freeze-trapping this enzyme during Ar turnover captured the key catalytic intermediate in high occupancy, denoted E₄(4H), which has accumulated 4[e^?/H⁺] as two bridging hydrides, Fe2–H–Fe6 and Fe3–H–Fe7, and protons bound to two sulfurs. E₄(4H) is poised to bind/reduce N₂ as driven by mechanistically-coupled H₂ reductive-elimination of the hydrides. This process must compete with ongoing hydride protonation (HP), which releases H₂ as the enzyme relaxes to state E₂(2H), containing 2[e^?/H⁺] as a hydride and sulfur-bound proton; accumulation of E₄(4H) in α-V70I is enhanced by HP suppression. EPR and ⁹⁵Mo ENDOR spectroscopies now show that resting-state α-V70I enzyme exists in two conformational states, both in solution and as crystallized, one with wild type (WT)-like FeMo-co and one with perturbed FeMo-co. These reflect two conformations of the Ile residue, as visualized in a reanalysis of the X-ray diffraction data of α-V70I and confirmed by computations. EPR measurements show delivery of 2[e^?/H⁺] to the E₀ state of the WT MoFe protein and to both α-V70I conformations generating E₂(2H) that contains the Fe3–H–Fe7 bridging hydride; accumulation of another 2[e^?/H⁺] generates E₄(4H) with Fe2–H–Fe6 as the second hydride. E₄(4H) in WT enzyme and a minority α-V70I E₄(4H) conformation as visualized by QM/MM computations relax to resting-state through two HP steps that reverse the formation process: HP of Fe2–H–Fe6 followed by slower HP of Fe3–H–Fe7, which leads to transient accumulation of E₂(2H) containing Fe3–H–Fe7. In the dominant α-V70I E₄(4H) conformation, HP of Fe2–H–Fe6 is passively suppressed by the positioning of the Ile sidechain; slow HP of Fe3–H–Fe7 occurs first and the resulting E₂(2H) contains Fe2–H–Fe6. It is this HP suppression in E₄(4H) that enables α-V70I MoFe to accumulate E₄(4H) in high occupancy. In addition, HP suppression in α-V70I E₄(4H) kinetically unmasks hydride reductive-elimination without N₂-binding, a process that is precluded in WT enzyme.