Cobalt Porphyrin Research Articles

Controlling Radical-Type Single-Electron Elementary Steps in Catalysis with Redox-Active Ligands and Substrates.

Advances in (spectroscopic) characterization of the unusual electronic structures of open-shell cobalt complexes bearing redox-active ligands, combined with detailed mapping of their reactivity, have uncovered several new catalytic radical-type protocols that make efficient use of the synergistic properties of redox-active ligands, redox-active substrates, and the metal to which they coordinate. In this perspective, we discuss the tools available to study, induce, and control catalytic radical-type reactions with redox-active ligands and/or substrates, contemplating recent developments in the field, including some noteworthy tools, methods, and reactions developed in our own group. The main topics covered are (i) tools to characterize redox-active ligands; (ii) novel synthetic applications of catalytic reactions that make use of redox-active carbene and nitrene substrates at open-shell cobalt–porphyrins; (iii) development of catalytic reactions that take advantage of purely ligand- and substrate-based redox processes, coupled to cobalt-centered spin-changing events in a synergistic manner; and (iv) utilization of redox-active ligands to influence the spin state of the metal. Redox-active ligands have emerged as useful tools to generate and control reactive metal-coordinated radicals, which give access to new synthetic methodologies and intricate (electronic) structures, some of which are yet to be exposed.

Highly Active Electrocatalyst Derived from ZIF-8 Decorated with Iron(III) and Cobalt(III) Porphyrin Toward Efficient Oxygen Reduction in Both Alkaline and Acidic Media

Highly Active Electrocatalyst Derived from ZIF-8 Decorated with Iron(III) and Cobalt(III) Porphyrin Toward Efficient Oxygen Reduction in Both Alkaline and Acidic Media

High-performance and wearable hazardous gases sensor based on n-n heterojunction film of NGO and tetrakis(1-pyrenyl)porphyrin

The popularity of “Internet of Things” and portable electronic devices creates unprecedented demands for wearable gas sensors with excellent performance. In this study, the flexible n-n heterojunction film is firstly produced from metalloporphyrin complex 5,10,15,20-tetrakis(1-pyrenyl) porphyrin cobalt (II) (CoTPyrP) and nitrogen-doped graphene oxide (NGO) film, using solution-processing quasi-Langmuir–Shäfer (QLS) method and employed as the electrochemical identification layer for the wearable sensor. Thanks to the attractive electron-transfer properties from porphyrin to NGO, and the local regulation of electron transport by N and C atoms with different electronegativity on NGO, the resulting sensor shows good responses to NO2, SO2, NH3, H2S gases with the low detection limit (LOD) of 6, 74, 113 and 178 ppb, respectively. The uniform and compact structure of the heterojunction films provide excellent mechanical flexibility and suppress the penetration of gases into the film to obtain fast recovery speed. In addition, a sensor array consisting of NGO/CoTPyrP heterojunction and CoTPyrP film sensor is established, achieving selective identification of four hazardous gases. The present work provides potential application for hazardous gases identification in actual systems, and proposes an effective method to develop new flexible n-n heterojunctions for wearable gas sensors.

Revisiting the Electronic Structure of Cobalt Porphyrin Nitrene and Carbene Radicals with NEVPT2-CASSCF Calculations: Doublet versus Quartet Ground States.

Cobalt porphyrin complexes are established catalysts for carbene and nitrene radical group-transfer reactions. The key carbene and mono- and bisnitrene radical complexes coordinated to [Co(TPP)] (TPP = tetraphenylporphyrin) have previously been investigated with a variety of experimental techniques and supporting (single-reference) density functional theory (DFT) calculations that indicated doublet (S = 1/2) ground states for all three species. In this contribution, we revisit their electronic structures with multireference N-electron valence state perturbation theory (NEVPT2)-complete-active-space self-consistent-field (CASSCF) calculations to investigate possible multireference contributions to the ground-state wave functions. The carbene ([CoIII(TPP)(•CHCO2Et)]) and mononitrene ([CoIII(TPP)(•NNs)]) radical complexes were confirmed to have uncomplicated doublet ground states, although a higher carbene or nitrene radical character and a lower Co–C/N bond order was found in the NEVPT2-CASSCF calculations. Supported by electron paramagnetic resonance analysis and spin counting, paramagnetic molar susceptibility determination, and NEVPT2-CASSCF calculations, we report that the cobalt porphyrin bisnitrene complex ([CoIII(TPP•)(•NNs)2]) has a quartet (S = 3/2) spin ground state, with a thermally accesible multireference and multideterminant “broken-symmetry” doublet spin excited state. A spin flip on the porphyrin-centered unpaired electron allows for interconversion between the quartet and broken-symmetry doublet spin states, with an approximate 10-fold higher Boltzmann population of the quartet at room temperature.

Mechanism and kinetics of the aerobic oxidation of benzyl alcohol to benzaldehyde catalyzed by cobalt porphyrin in a membrane microchannel reactor

The highly efficient selective aerobic oxidation of benzyl alcohol to benzaldehyde catalyzed by cobalt porphyrin was achieved in a membrane microchannel reactor. The efficiency of benzyl alcohol oxidation was remarkably improved in the micro-structured chemical system, achieving a conversion and benzaldehyde selectivity of 82% and 98%, respectively, in 6.5 min. The classification and transfer of free radicals, as well as the oxygen-transfer mechanism, were determined by in situ EPR (electron paramagnetic resonance) and in situ UV–visible spectroscopy. Further kinetic studies revealed that the oxidation of benzyl alcohol follows the Michaelis–Menten kinetics, with Km = 0.133 mol/L.A mathematic kinetic model was proposed, and the kinetic model fitted the experimental data well. The mathematical model can predict the reaction process at a wide range of benzyl alcohol concentrations, which is beneficial for the process optimization and reactor design.

(Invited) Strategies in Colloidal Catalysis for Generation of Solar Fuels

This talk will describe two separate strategies to use colloidal semiconductor nanocrystals to photocatalytically produce (i) the fuel intermediate CO from the abundant feedstock CO2, and (ii) H2 from protons within a hydrogel with pH-dependent structure. CO2 reduction is accomplished with record turnover in pure water with a combination of colloidal CuInS2 nanocrystals and a cobalt porphyrin electrocatalyst. The nanocrystals are decorated with partially protonated amine-terminated ligands, which not only provide a means of electrostatic self-assembly with the negatively charge porphyrin, but also allow pre-activation of the CO2 through formation of carbamic acid. In a separate system based on cadmium chalcogenide nanorods, the yield of proton reduction is non-monotonically dependent on the pH of the hydrogel with a large spike near the pKa of the exposed amine groups within the gel.

Quantifying Reversible Nitrogenous Ligand Binding to Co(II) Porphyrin Receptors at the Solution/Solid Interface and in Solution

We present a quantitative study comparing the binding of 4-methoxypyridine, MeOPy, ligand to Co(II)octaethylporphyrin, CoOEP, at the phenyloctane/HOPG interface and in toluene solution. Scanning tunneling microscopy (STM) was used to monitor ligand binding to the porphyrin receptors adsorbed on graphite with single-molecule resolution. Electronic spectroscopy was employed for examining this process in fluid solution. The on-surface coordination reaction was completely reversible and followed a simple Langmuir adsorption isotherm. Ligand affinities (or ΔG) for the binding processes in the two different chemical environments were determined from the respective equilibrium constants. The free energy value of -13.0±0.3 kJ/mol for the ligation reaction of MeOPy to CoOEP at the solution/HOPG interface is less negative than the ΔG for cobalt porphyrin complexed to the ligand in solution, -16.8±0.2 kJ/mole. This result indicates that the MeOPy-CoOEP complex is more stable in solution than on the surface. Additional thermodynamic values for the formation of the surface ligated species (ΔHc = -50 kJ/mol and ΔSc = -120 J/mol) were extracted from temperature dependent STM measurements. Density functional computational methods were also employed to explore the energetics of both the solution and surface reactions. At high concentrations of MeOPy the monolayer was observed to be stripped from the surface. Computational results indicate that this is not because of a reduction in adsorption energy of the MeOPy-CoOEP complex. Nearest neighbor analysis of the MeOPy-CoOEP in the STM images revealed positive cooperative ligand binding behavior. Our studies bring new insights to the general principles of affinity and cooperativity in the ligand-receptor interactions at the solution/solid interface. Future applications of STM will pave the way for new strategies designing highly functional multisite receptor systems for sensing, catalysis, and pharmacological applications.

Earth-Abundant Electrocatalysts for the Oxygen Evolution Reaction of Water Splitting Using Nanostructured Layered Inorganic Materials

Nature uses solar energy and earth-abundant materials for splitting water into oxygen, in the oxygen evolution reaction (OER), and protons, which are then reduced into hydrogen in the hydrogen evolution reaction (HER). Hydrogen solar fuel produced in artificial photosynthesis schemes for water splitting could be used in fuel cells. Learning from nature, instead of using expensive catalysts such as platinum, cheaper alternatives (such as cobalt, iron, or nickel) would provide the opportunity to make solar energy even more competitive with fossil fuels. However, obtaining efficient catalysts based on earth-abundant materials is still a daunting task, particularly for the OER. Recent theory has shown that nanoscopic confinement of catalysts increases the stability and efficiency of catalysts for OER. We have designed and develop earth-abundant electrocatalysts for oxygen reduction and water splitting using nanostructured layered inorganic materials of zirconium phosphate (ZrP). We have demonstrated improved electrocatalytic activity of ZrP nanomaterials loaded with metal ions suitable for the OER of water splitting. Adsorbing Co or Ni catalysts on the ZrP nanoparticles surface proved to improved OER activity compared to intercalated catalysts. A comparison between adsorbed Co or Ni catalysts and those catalysts on exfoliated ZrP hexagonal nanoplatelets proved that those on exfoliated nanoplatelets were more active, with diminished overpotentials and reduced Tafel plot slopes as well as higher mass activities. More recently, comparison between Co and Ni catalyst on ZrP particles with different morphologies (hexagonal platelets, rods, cubes, and spheres) revealed that the more active Co catalysts are those on hexagonal ZrP platelets, whereas the best Ni catalysts are those on ZrP spheres. Finally, encouraging recent results with a cobalt porphyrin catalyst will be presented, as well as recent XAS operando results. These results demonstrate that ZrP nanoparticles are suitable supports for electrocatalysis of the OER and water splitting.Sponsored by NSF Center for Chemical Innovation in Solar Fuels CHE-1305124 and NSF-PREM Center for Interfacial Electrochemistry for Energy Materials (CIE2M) grant DMR-1827622.

Regulating the type of cobalt porphyrins for synergistic promotion of photoelectrochemical water splitting of BiVO4

Three novel semiconductor composite photoanodes (BiVO4/GO/CoTPP(OH)n, n = 1, 4 and 8) are designed and prepared by decorating BiVO4 with graphene oxide (GO) and cobalt porphyrins bearing different number of hydroxyl groups. The introduction of GO and CoTPP(OH)n onto the BiVO4 surface has been confirmed by transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Fourier transform infrared and Raman spectroscopic techniques, endowing BiVO4 with improved charge transfer and broadened light absorption ability. Their viability as photoelectrochemical system is investigated under AM 1.5 G light irradiation, the photoelectrochemical water splitting performance being found to be dependent on the type of cobalt porphyrins. The BiVO4/GO/CoTPP(OH)4 is found to exhibit the largest photocurrent density of 5.27 mA/cm−2 at 1.23 V vs. RHE due to a combination of mechanisms.

A Supramolecular Porous Organic Cage Platform Promotes Electrochemical Hydrogen Evolution from Water Catalyzed by Cobalt Porphyrins

AbstractWe report a supramolecular porous organic cage platform composed of cobalt porphyrins for catalyzing the electrochemical hydrogen evolution reaction (HER) from water at neutral pH. Owing to its permanent porosity, the supramolecular structure yields a catalyst film with a fivefold increase in the number of electrochemically active cobalt atoms and an improvement in Tafel slope from 170 mV/decade to 119 mV/decade compared to a planar cobalt porphyrin analog, reaching activities over 19,000 turnovers for HER over a 24‐hour period with 100 % Faradaic efficiency.

Electropolymerization of cobalt porphyrins and corroles for the oxygen evolution reaction

Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction (OER) is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a simple and fast electropolymerization method. Our results showed that Co-1-P@CC, formed by electropolymerizing Co tetrakis(p-N-pyrrolylphenyl)porphyrin (Co-1-P) on carbon cloth (CC), is the most active OER catalyst in the examined Co porphyrins and corroles in alkaline aqueous solutions by displaying an onset overpotential of 380 mV. Long-term electrolysis tests confirmed the stability of these electropolymerized films by functioning as OER electrocatalysts.

Electrochemical characterization of β,β′-butanoporphyrins containing sterically hinderedmeso-2,6-dihalogenophenyl substituents and first-row transition metal ions in nonaqueous media

Six [Formula: see text],[Formula: see text]-butano substituted metalloporphyrins containing sterically hindered meso-dihalogenophenyl substituents and first-row transition metal ions were synthesized and their electrochemical and spectroelectrochemical properties were characterized in nonaqueous media. The investigated compounds have the general formula butano(Y2Ph)4PorM, where Por is a dianion of the porphyrin, M = Mn[Formula: see text]Cl, Fe[Formula: see text]Cl, Co[Formula: see text], Ni[Formula: see text], Cu[Formula: see text] or Zn[Formula: see text]and Y2Ph is a sterically hindered 2,6-F2Ph or 2,6-Cl2Ph group on each of the four meso-positions of the macrocycle. The electrochemistry of each porphyrin was examined in CH2Cl2or pyridine containing 0.1 M tetra-[Formula: see text]-butylammonium perchlorate. The first one-electron reduction is metal-centered for the manganese(III), iron(III) and cobalt(II) porphyrins to generate the Mn(II), Fe(II) and Co(I) porphyrins, but it is porphyrin ring-centered for the other examined M(II) porphyrins to give porphyrin [Formula: see text]-anion radicals under the given solution conditions. The effect of the [Formula: see text],[Formula: see text]-butano and sterically hindered meso-Y2Ph substituents on redox potentials and electron transfer mechanisms are discussed and compared to what was previously reported for butano-substituted tetraarylporphyrins without hindered meso-substituents.

Cobalt(II)porphyrin-Mediated Selective Synthesis of 1,5-Diketones via an Interrupted-Borrowing Hydrogen Strategy Using Methanol as a C1 Source.

A novel cobalt(II)porphyrin-mediated acceptorless dehydrogenation of methanol is reported for the first time. This methodology has been applied for the coupling of a variety of ketones with methanol to produce 1,5-diketones along with H2 and H2O as the environment friendly byproducts. This paradigm was also demonstrated for a one-pot synthesis of substituted pyridines using a sequential addition protocol where the 1,5-diketones were generated in situ. From many experiments including those involving deuterium labeling, it is proposed that protonated cobalt(II)porphyrin methoxide complex acts as an intermediate to generate formaldehyde along with a metal hydride.

Back Cover: Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two‐Electron and Four‐Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers (Angew. Chem. Int. Ed. 23/2021)

Back Cover: Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two‐Electron and Four‐Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers (Angew. Chem. Int. Ed. 23/2021)

A colorimetric paper-based optode sensor for highly sensitive and selective determination of thiocyanate in urine sample using cobalt porphyrin derivative

In this work, a highly sensitive colorimetric paper-based optode for the determination of thiocyanate in urine samples was developed for the first time. The cocktail solution of the optode was composed of 5,10,15,20-tetrakis(4-octyloxyphenyl)porphyrin cobalt(II) complex (L), tridodecylmethylammonium chloride (TDMACl), 2-nitrophenyl octyl ether, and polyvinyl chloride as an ionophore, an ion exchanger, a plasticizer, and a polymer, respectively. The paper-based optode responded to thiocyanate by increasing the blue component in the RGB index and a visible change, with the naked-eye, of the optode color from pink to green was observed. From the central composite design, the optimized conditions that yielded the highest sensitivity were 4.70 mmol/kg TDMACl and 13.75 mmol/kg L. The developed optode sensor was highly selective and responded to thiocyanate over other anions, with a working range of 0.001–5 mM and with a coefficient of determination (R2) of 0.9915. The limits of detection using naked-eye and camera were determined to be 50.0 μM and 1.26 μM, respectively. In addition, the LOD and LOQ estimated from the standard deviation of the blank were 0.65 and 1.87 μM, respectively. Furthermore, this sensor was successfully applied to the detection of thiocyanate in urine samples from non-smokers and smokers. The results were in good agreement with the standard ion chromatography (IC) technique. This developed paper-based optode sensor was simple, low-cost, portable, and easy to use as a sensing device without any complicated instrument.

Three cobalt(II) porphyrins ligated with pyridyl-containing nanocarbon/gold(III) porphyrin for solar cells: Synthesis and characterization

Three new donor–acceptor systems, synthesized by axial coordination of 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero[60]pyrrolidine (PyC60)/2,5-di-(pyridin-2-yl)-3,4-fullero[70]pyrrolidine (Py2C70) and meso-tetra(4-pyridyl)porphyrinato)gold(III) chloride (ClAuP) with (meso-tetra(4-octyloxyphenyl)porphyrinato)cobalt(II) (CoP) were observed. In order to optimize the reaction conditions, the formation mechanism and composition of the complexes dependent on the structure of axial molecular ligand were explored. The triad, (PyC60)2CoP/(Py2C70)2CoP, and dyad, (ClAuP)CoP, were formed respectively in the two-stage and one-stage process. The confirmation of their chemical structure and determination of stability constants was performed using the UV–vis, IR, 1H NMR, MS (MALDI-TOF) spectrometry and chemical thermodynamics/kinetics, respectively. Photoelectrochemical studies of the porphyrin-fullerene/porphyrin-porphyrin systems were carried out compared with corresponding precursors by the amperometry methods. The high values of the photocurrent density and incident photon energy conversion to current (IPCE365nm) of the titanium electrode modified by (PyC60)2CoP/(Py2C70)2CoP/(ClAuP)CoP were demonstrated, which points to good perspectives in the application of the coordination complexes synthesized as a photoactive molecular material for solar cells.

Donor-acceptor conjugates derived from cobalt porphyrin and fullerene via metal-ligand axial coordination: Formation and excited state charge separation

Two types of cobalt porphyrins, viz., meso-tetrakis(tolylporphyrinato)cobalt(II), (TTP)Co (1), and meso-tetrakis(triphenylamino porphyrinato)cobalt(II), [(TPA)4P]Co, (2) were self-assembled via metal-ligand axial coordination of phenyl imidazole functionalized fulleropyrrolidine, ImC[Formula: see text] to form a new series of donor–acceptor constructs. A 1:2 complex formation with ImC[Formula: see text] was established in the case of (TTP)Co while for [(TPA)4P]Co only a 1:1 complex was possible to positively identify. The binding constants [Formula: see text] and [Formula: see text] for step-wise addition of ImC[Formula: see text] to (TTP)Co were found to be 1.07 × 105 and 3.20 × 104 M[Formula: see text], respectively. For [(TPA)4P]Co:ImC[Formula: see text], the measured [Formula: see text] values was found to be 6.48 × 104 M[Formula: see text], slightly smaller than that observed for (TTP)Co. Although both cobalt porphyrins were non-fluorescent, they were able to quench the fluorescence of ImC[Formula: see text] indicating occurrence of excited state events in the supramolecular donor-acceptor complexes. Electrochemistry coupled with spectroelectrochemistry, revealed the formation of cobalt(III) porphyrin cation instead of a cobalt(II) porphyrin radical cation, as the main product, during oxidation of phenyl imidazole coordinated cobalt porphyrin. With the help of computational and electrochemical results, an energy level diagram was constructed to witness excited state photo-events. Competitive energy and electron transfer from excited CoP to coordinated ImC[Formula: see text], and electron transfer from Im1C[Formula: see text]* to cobalt(II) porphyrin resulting into the formation of PCo[Formula: see text]:ImC[Formula: see text] charge separated state was possible to envision from the energy diagram. Finally, using femtosecond transient absorption spectroscopy and data analysis by Glotaran, it was possible to establish sequential occurrence of energy transfer and charge separation processes. The lifetime of the final charge separated state was [Formula: see text] 2 ns. A slightly better charge stabilization was observed in the case of [(TPA)4P]Co:ImC[Formula: see text] due to the presence of electron rich, peripheral triphenylamine substituents on the cobalt porphyrin.

Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two‐Electron and Four‐Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers

AbstractAchieving a selective 2 e− or 4 e− oxygen reduction reaction (ORR) is critical but challenging. Herein, we report controlling ORR selectivity of Co porphyrins by tuning only steric effects. We designed Co porphyrin 1 with meso‐phenyls each bearing a bulky ortho‐amido group. Due to the resulted steric hinderance, 1 has four atropisomers with similar electronic structures but dissimilar steric effects. Isomers αβαβ and αααα catalyze ORR with n=2.10 and 3.75 (n is the electron number transferred per O2), respectively, but ααββ and αααβ show poor selectivity with n=2.89–3.10. Isomer αβαβ catalyzes 2 e− ORR by preventing a bimolecular O2 activation path, while αααα improves 4 e− ORR selectivity by improving O2 binding at its pocket, a feature confirmed by spectroscopy methods, including O K‐edge near‐edge X‐ray absorption fine structure. This work represents an unparalleled example to improve 2 e− and 4 e− ORR by tuning only steric effects without changing molecular and electronic structures.

Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two-Electron and Four-Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers.

Achieving a selective 2 e- or 4 e- oxygen reduction reaction (ORR) is critical but challenging. Herein, we report controlling ORR selectivity of Co porphyrins by tuning only steric effects. We designed Co porphyrin 1 with meso-phenyls each bearing a bulky ortho-amido group. Due to the resulted steric hinderance, 1 has four atropisomers with similar electronic structures but dissimilar steric effects. Isomers αβαβ and αααα catalyze ORR with n=2.10 and 3.75 (n is the electron number transferred per O2 ), respectively, but ααββ and αααβ show poor selectivity with n=2.89-3.10. Isomer αβαβ catalyzes 2 e- ORR by preventing a bimolecular O2 activation path, while αααα improves 4 e- ORR selectivity by improving O2 binding at its pocket, a feature confirmed by spectroscopy methods, including O K-edge near-edge X-ray absorption fine structure. This work represents an unparalleled example to improve 2 e- and 4 e- ORR by tuning only steric effects without changing molecular and electronic structures.

Light-Driven CO2 Reduction by Co-Cytochrome b 562.

The current trend in atmospheric carbon dioxide concentrations is causing increasing concerns for its environmental impacts, and spurring the developments of sustainable methods to reduce CO2 to usable molecules. We report the light-driven CO2 reduction in water in mild conditions by artificial protein catalysts based on cytochrome b 562 and incorporating cobalt protoporphyrin IX as cofactor. Incorporation into the protein scaffolds enhances the intrinsic reactivity of the cobalt porphyrin toward proton reduction and CO generation. Mutations around the binding site modulate the activity of the enzyme, pointing to the possibility of further improving catalytic activity through rational design or directed evolution.