210 research outputs found
Computational investigations of homogeneous catalysis and spin-state energetics in Fe(II) and Co(III) complexes
This thesis focuses on the testing and use of quantum-chemical modelling to describe and study Fe(II) and Co(III) complexes, and in particular their spin-state behaviour and efficacy in homogeneous catalysis.
An Fe(II)-catalysed transfer-hydrogenation reaction was investigated with density functional theory (DFT). This project was in close collaboration with experimentalists in the Webster group at the University of Bath. To ensure an accurate approach was employed, a rigorous benchmarking evaluation was carried out against available and closely related experimental data (Chapter 2). This identified a reliable DFT approach to study the catalytic transfer-hydrogenation reaction with (Chapter 3). Modelling of this reaction revealed that careful assessment of the chemical model was required to account fully for the experimental observations, namely in accounting for a selectivity towards transfer-hydrogenation over hydroboration and dehydrocoupling. The identification of supramolecular oligomerization of reagents was an important component of the final chemical model.
The other reaction of interest in this work is Co(III) carboxylate-assisted C–H functionalization. In this case, a benchmarking study against experimentally-derived spin-state energetics of Co(III) complexes was carried out to evaluate quantum-chemical approaches in the context of Co(III) catalysis (Chapter 4). DFT, NEVPT2 and DLPNO-CCSD(T) were assessed in this regard, and DLPNO-CCSD(T) was found to be the most accurate performer of the three types of methods. This level of theory was then used to yield reference energetics when looking at an archetypal Co(III) carboxylate-assisted C–H functionalization reaction, and against this reference profile, the performance of DFT was assessed (Chapter 5). This identified a computational protocol which allowed for the modelling and assessment of the full catalytic C–H functionalization reaction
Accurate computed spin-state energetics for Co(iii) complexes:implications for modelling homogeneous catalysis
Co(III) complexes are increasingly prevalent in homogeneous catalysis. Catalytic cycles involve multiple intermediates, many of which will feature unsaturated metal centres. This raises the possibility of multistate character along reaction pathways and so requires an accurate approach to calculating spin-state energetics. Here we report an assessment of the performance of DLPNO-CCSD(T) (domain-based local pair natural orbital approximation to coupled cluster theory) against experimental Co-1 to Co-3 spin splitting energies for a series of pseudo-octahedral Co(III) complexes. The alternative NEVPT2 (strongly-contracted n-electron valence perturbation theory) and a range of density functionals are also assessed. DLPNO-CCSD(T) is identified as a highly promising method, with mean absolute deviations (MADs) as small as 1.3 kcal mol(-1) when Kohn-Sham reference orbitals are used. DLPNO-CCSD(T) out-performs NEVPT2 for which a MAD of 3.5 kcal mol(-)(1 )can be achieved when a (10,12) active space is employed. Of the nine DFT methods investigated TPSS is the leading functional, with a MAD of 1.9 kcal mol(-1). Our results show how DLPNO-CCSD(T) can provide accurate spin state energetics for Co(III) species in particular and first row transition metal systems in general. DLPNO-CCSD(T) is therefore a promising method for applications in the burgeoning field of homogeneous catalysis based on Co(III) species
Development of novel catalytic solutions applied for the hydrogen evolution and oxygen reduction reactions
This thesis reports the utilisation of 2D nanomaterials, namely molybdenum disulphide (2D-MoS2) and molybdenum diselenide (2D-MoSe2), as cheap, earth abundant and effective catalytic alternatives to platinum (Pt) for hydrogen production (via the hydrogen evolution reaction (HER)) within electrolysers and energy generation (via the oxygen reduction reaction (ORR)) within proton exchange membrane fuel cells (PEMFC). Chapter 1 introduces the chemical reactions associated with electrolysers and PEMFCs, then gives an overview of the relevant fundamental electrochemical concepts utilised throughout this thesis. Subsequent to this, Chapter 2 specifically describes the equipment and fabrication techniques implemented herein, in addition to providing the full physicochemical characterisation of the 2D-MoS2 and 2D-MoSe2 utilised in later chapters.
Chapter 3 demonstrates that a commonly employed surfactant (sodium cholate) used in the liquid exfoliation of 2D-MoS2 has a profound effect upon its electrocatalytic activity. It is shown that the surfactant has a negative effect upon the observed HER signal output (decreasing the current density and increasing the electronegativity of the HER onset potential) of the 2D-MoS2 compared to “pristine” 2D-MoS2 (produced without a surfactant present). This suggests that future studies utilising 2D nanomaterials should carefully consider their use of a surfactant as well as perform the necessary control experiments. Chapters 4 and 5 reveal that, in specific conditions, 2D-MoS2 nanosheets are effective at reducing the electronegativity of the HER and ORR onset potentials, increasing their achievable current density and allowing the ORR reaction mechanism to occur via the desirable 4 electron process (product: H2O). This electrocatalytic effect is reported herein for the first time. Research was undertaken by electrically wiring the 2D-MoS2 to four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE). The reduction in the electronegativity of the HER and ORR onset potential is shown to be associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct from the literature, which predominately uses just GC as a supporting electrode material. It is revealed that the ability to catalyse the HER and ORR is dependent on the mass deposited until a critical coverage of 2D-MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail.
In Chapter 6, 2D-MoS2 screen-printed electrodes (2D-MoS2-SPEs) are designed, fabricated and their performance is evaluated towards the electrochemical HER and ORR within acidic aqueous media. A screen-printable ink is developed, which allows for the tailoring of the 2D-MoS2 content/mass used in the fabrication of the 2D-MoS2-SPEs. The 2D-MoS2-SPEs are shown to exhibit an electrocatalytic behaviour towards the ORR, which is found, critically, to be reliant upon the percentage mass incorporation of 2D-MoS2 in the 2D-MoS2-SPEs. Chapter 7 utilises the exact methodology for electrocatalytic ink production as Chapter 6, however it incorporates 2D-MoSe2 and explores the fabricated 2D-MoSe2-SPEs towards the HER where beneficial electrochemistry is observed. Both the 2D-MoS2-SPEs and 2D-MoSe2-SPEs display remarkable stability with no degradation in their respective performances over the course of 1000 repeat scans. The electrocatalytic inks produced in these chapters and the resultant mass producible electrodes mitigate the need to post hoc modify an electrode via the drop-casting technique that has been shown to result in poor stability.
This thesis reports that novel 2D nanomaterials can be implemented as beneficial electrode materials towards enhancing “green” energy generation technologies. Specifically, 2D-MoS2 is shown to be effective at lowering the onset potential and increasing the achievable current density for the HER and ORR, giving rise to further benefits when 2D-MoS2 (and 2D-MoSe2 towards the HER) are incorporated into SPEs. These novel electrodes exhibit the inherent unique electrochemical behaviour of the 2D nanomaterials incorporated and benefit from the remarkable stability attributed to the intrinsic properties of a SPE. Consequently, the findings of this thesis are highly applicable to industrial electrolyser/fuel cell applications
Room temperature iron-catalyzed transfer hydrogenation and regioselective deuteration of carbon-carbon double bonds
An iron catalyst has been developed for the transfer hydrogenation of carbon-carbon multiple bonds. Using a well-defined β-diketiminate iron(II) precatalyst, a sacrificial amine and a borane, even simple, unactivated alkenes such as 1-hexene undergo hydrogenation within 1 h at room temperature. Tuning the reagent stoichiometry allows for semi- and complete hydrogenation of terminal alkynes. It is also possible to hydrogenate aminoalkenes and aminoalkynes without poisoning the catalyst through competitive amine ligation. Furthermore, by exploiting the separate protic and hydridic nature of the reagents, it is possible to regioselectively prepare monoisotopically labeled products. DFT calculations define a mechanism for the transfer hydrogenation of propene with nBuNH 2 and HBpin that involves the initial formation of an iron(II)-hydride active species, 1,2-insertion of propene, and rate-limiting protonolysis of the resultant alkyl by the amine N-H bond. This mechanism is fully consistent with the selective deuteration studies, although the calculations also highlight alkene hydroboration and amine-borane dehydrocoupling as competitive processes. This was resolved by reassessing the nature of the active transfer hydrogenation agent: experimentally, a gel is observed in catalysis, and calculations suggest this can be formulated as an oligomeric species comprising H-bonded amine-borane adducts. Gel formation serves to reduce the effective concentrations of free HBpin and nBuNH 2 and so disfavors both hydroboration and dehydrocoupling while allowing alkene migratory insertion (and hence transfer hydrogenation) to dominate. </p
Reductive Elimination at Carbon under Steric Control
It has been previously demonstrated that stable singlet electrophilic carbenes can behave as metal surrogates in the activation of strong E-H bonds (E = H, B, N, Si, P), but it was believed that these activations only proceed through an irreversible activation barrier. Herein we show that, as is the case with transition metals, the steric environment can be used to promote reductive elimination at carbon centers
Phosphirenium Ions as Masked Phosphenium Catalysts:Mechanistic Evaluation and Application in Synthesis
The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a "masked phosphenium"source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, Hâ'SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electrondonating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies.</p
Phosphirenium ions as masked phosphenium catalysts : mechanistic evaluation and application in synthesis
The EPSRC is thanked for funding. S.E.N. thanks Heriot Watt University for the award of a James Watt scholarship.The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a "masked phosphenium"source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, Hâ'SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electrondonating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies.Peer reviewe
A 128×120 5-Wire 1.96mm2 40nm/90nm 3D Stacked SPAD Time Resolved Image Sensor SoC for Microendoscopy
Enhancing the efficiency of the hydrogen evolution reaction utilising Fe3P bulk modified screen-printed electrodes via the application of a magnetic field
We report the fabrication and optimisation of Fe3P bulk modified screen-printed electrochemical platforms (SPEs) for the hydrogen evolution reaction (HER) within acidic media. We optimise the achievable current density towards the HER of the Fe3P SPEs by utilising ball-milled Fe3P variants and increasing the mass percentage of Fe3P incorporated into the SPEs. Additionally, the synergy of the application of a variable weak (constant) external magnetic field (330 mT to 40 mT) beneficially augments the current density output by 56%. This paper not only highlights the benefits of physical catalyst optimisation but also demonstrates a methodology to further enhance the cathodic efficiency of the HER with the facile application of a weak (constant) magnetic field
MoS2-graphene-CuNi2S4 nanocomposite an efficient electrocatalyst for the hydrogen evolution reaction
We present a facile methodology for the synthesis of a novel 2D-MoS2, graphene and CuNi2S4 (MoS2-g-CuNi2S4) nanocomposite that displays highly efficient electrocatalytic activity towards the production of hydrogen. The intrinsic hydrogen evolution reaction (HER) activity of MoS2 nanosheets was significantly enhanced by increasing the affinity of the active edge sites towards Hþ adsorption using transition metal (Cu and Ni2) dopants, whilst also increasing the edge sites exposure by anchoring them to a graphene frame- work. Detailed XPS analysis reveals a higher percentage of surface exposed S at 17.04%, of which 48.83% is metal bonded S (sulfide). The resultant MoS2-g-CuNi2S4 nanocomposites are immobilized upon screen-printed electrodes (SPEs) and exhibit a HER onset potential and Tafel slope value of -0.05 V (vs. RHE) and 29.3 mV dec-1, respectively. These values are close to that of the polycrystalline Pt electrode (near zero potential (vs. RHE) and 21.0 mV dec-1, respectively) and enhanced over a bare/unmodified SPE (-0.43 V (vs. RHE) and 149.1 mV dec-1, respectively). Given the efficient, HER activity displayed by the novel MoS2-g-CuNi2S4/SPE electrochemical platform and the comparatively low associated cost of production for this nanocomposite, it has potential to be a cost-effective alternative to Pt within electrolyser technologies
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