Revealing Significant Electronic Effects on the Oxygen Reduction Reaction with Iron Porphyrins.

Understanding electronic effects on catalysis from a mechanism point of view is of fundamental significance but is also challenging. We herein report on electronic effects on the oxygen reduction reaction (ORR) with Fe porphyrins. By using FeIII tetraphenylporphyrin (TPP-Fe) and FeIII tetra(pentafluorophenyl)porphyrin (TPFP-Fe), we showed their different electrochemical and chemical behaviors for ORR. Mechanism studies revealed that the FeIII-superoxo species of TPP-Fe can undergo smooth protonation with trifluoroacetic acid (TFA) but the electron-deficient FeIII-superoxo species of TPFP-Fe cannot be protonated with TFA. The FeIII-superoxo reactivity difference between TPP-Fe and TPFP-Fe is the origin of their different catalytic ORR behaviors.

Adapting Synthetic Models of Heme/Cu Sites to Energy-Efficient Electrocatalytic Oxygen Reduction Reaction.

In nature, cytochrome c oxidases catalyze the 4e- oxygen reduction reaction (ORR) at the heme/Cu site, in which CuI is used to assist O2 activation. Because of the thermodynamic barrier to generate CuI , synthetic Fe-porphyrin/Cu complexes usually show moderate electrocatalytic ORR activity. We herein report on a Co-corrole/Co complex 1-Co for energy-efficient electrocatalytic ORR. By hanging a CoII ion over Co corrole, 1-Co realizes electrocatalytic 4e- ORR with a half-wave potential of 0.89 V versus RHE, which is outstanding among corrole-based electrocatalysts. Notably, 1-Co outperforms Co corrole hanged with CuII or ZnII . We revealed that the hanging CoII ion can provide an electron to improve O2 binding thermodynamically and dynamically, a function represented by the biological CuI ion of the heme/Cu site. This work is significant to present a remarkable ORR electrocatalyst and to show the vital role of a second-sphere redox-active metal ion in promoting O2 binding and activation.

Coordination Tuning of Metal Porphyrins for Improved Oxygen Evolution Reaction.

The nucleophilic attack of water or hydroxide on metal-oxo units forms an O-O bond in the oxygen evolution reaction (OER). Coordination tuning to improve this attack is intriguing but has been rarely realized. We herein report on improved OER catalysis by metal porphyrin 1-M (M=Co, Fe) with a coordinatively unsaturated metal ion. We designed and synthesized 1-M by sterically blocking one porphyrin side with a tethered tetraazacyclododecane unit. With this protection, the metal-oxo species generated in OER can maintain an unoccupied trans axial site. Importantly, 1-M displays a higher OER activity in alkaline solutions than analogues lacking such an axial protection by decreasing up to 150-mV overpotential to achieve 10 mA/cm2 current density. Theoretical studies suggest that with an unoccupied trans axial site, the metal-oxo unit becomes more positively charged and thus is more favoured for the hydroxide nucleophilic attack as compared to metal-oxo units bearing trans axial ligands.

Electrocatalytic hydrogen evolution with a copper porphyrin bearing meso-(o-carborane) substituents.

A newly designed copper complex of 5,15-bis(pentafluorophenyl)-10,20-bis(o-carborane)porphyrin (1) was synthesized and tested for the electrocatalytic hydrogen evolution reaction (HER). In acetonitrile, 1 was much more efficient than Cu 5,15-bis(pentafluorophenyl)-10,20-diphenylporphyrin (2) for electrocatalytic HER by shifting the catalytic wave to the anodic direction by 190 mV. In aqueous media, 1 also outperformed 2 by achieving higher current densities under smaller overpotentials. This enhancement was attributed to the aromatic and the strong electron-withdrawing properties of o-carborane groups. This work is significant to address the crucial effects of meso-(o-carborane) substituents of metal porphyrins on boosting the electrocatalytic HER.

Effect of Proton Transfer on Electrocatalytic Water Oxidation by Manganese Phosphates.

The effect of proton transfer on water oxidation has hardly been measurably established in heterogeneous electrocatalysts. Herein, two isomorphous manganese phosphates (NH4 MnPO4 ⋅ H2 O and KMnPO4 ⋅ H2 O) were designed to form an ideal platform to study the effect of proton transfer on water oxidation. The hydrogen-bonding network in NH4 MnPO4 ⋅ H2 O has been proven to be solely responsible for its better activity. The differences of the proton transfer kinetics in the two materials indicate a fast proton hopping transfer process with a low activation energy in NH4 MnPO4 ⋅ H2 O. In addition, the hydrogen-bonding network can effectively promote the proton transfer between adjacent Mn sites and further stabilize the MnIII -OH intermediates. The faster proton transfer results in a higher proportion of zeroth-order in [H+ ] for OER. Thus, proton transfer-affected electrocatalytic water oxidation has been measurably observed to bring detailed insights into the mechanism of water oxidation.

Role-Specialized Division of Labor in CO2 Reduction with Doubly-Functionalized Iron Porphyrin Atropisomers.

In enzymes, the active site residues function differently to promote chemical reactions. Such a role-specialized division of labor has been rarely realized by synthetic catalysts. We report herein on catalytic CO2 reduction with Fe porphyrins decorated with two cationic N,N,N-trimethylbenzylamine groups in cis- or trans-arrangement. The cis-isomer outperforms the trans-isomer and reaches a TOFmax of 4.4×105  s-1 in acetonitrile using phenol proton source. Theoretical studies revealed that the two cationic units in the cis-isomer are more effective than a single cationic unit to improve the CO2 binding, and more importantly, they function differently but cooperatively to promote the C-O bond cleavage: one interacts with the CO2 -adduct, while the other one interacts with the phenol molecule through electrostatic interactions. This work therefore presents a significant example of synthetic catalysts, which boost chemical reactions using a role-specialized strategy for substrate activation.

Crucial Roles of a Pendant Imidazole Ligand of a Cobalt Porphyrin Complex in the Stoichiometric and Catalytic Reduction of Dioxygen.

A cobalt porphyrin complex with a pendant imidazole base ([(L1 )CoII ]) is an efficient catalyst for the homogeneous catalytic two-electron reduction of dioxygen by 1,1'-dimethylferrocene (Me2 Fc) in the presence of triflic acid (HOTf), as compared with a cobalt porphyrin complex without a pendant imidazole base ([(L2 )CoII ]). The pendant imidazole ligand plays a crucial role not only to provide an imidazolinium proton for proton-coupled electron transfer (PCET) from [(L1 )CoII ] to O2 in the presence of HOTf but also to facilitate electron transfer (ET) from [(L1 )CoII ] to O2 in the absence of HOTf. The kinetics analysis and the detection of intermediates in the stoichiometric and catalytic reduction of O2 have provided clues to clarify the crucial roles of the pendant imidazole ligand of [(L1 )CoII ] for the first time.

Metal-Corrole-Based Porous Organic Polymers for Electrocatalytic Oxygen Reduction and Evolution Reactions.

Integrating molecular catalysts into designed frameworks often enables improved catalysis. Compared with porphyrin-based frameworks, metal-corrole-based frameworks have been rarely developed, although monomeric metal corroles are usually more efficient than porphyrin counterparts for the electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). We herein report on metal-corrole-based porous organic polymers (POPs) as ORR and OER electrocatalysts. M-POPs (M=Mn, Fe, Co, Cu) were synthesized by coupling metal 10-phenyl-5,15-(4-iodophenyl)corrole with tetrakis(4-ethynylphenyl)methane. Compared with metal corrole monomers, M-POPs displayed significantly enhanced catalytic activity and stability. Co-POP outperformed other M-POPs by achieving four-electron ORR with a half-wave potential of 0.87 V vs. RHE and reaching 10 mA cm-2 OER current density at 340 mV overpotential. This work is unparalleled to develop and explore metal-corrole-based POPs as electrocatalysts.

Metalloporphyrins as Catalytic Models for Studying Hydrogen and Oxygen Evolution and Oxygen Reduction Reactions.

The hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) are involved in biological and artificial energy conversions. H-H and O-O bond formation/cleavage are essential steps in these reactions. In nature, intermediates involved in the H-H and O-O bond formation/cleavage are highly reactive and short-lived, making their identification and investigation difficult. In artificial catalysis, the realization of these reactions at considerable rates and close to their thermodynamic reaction equilibria remains a challenge. Therefore, the elucidation of the reaction mechanisms and structure-function relationships is of fundamental significance to understand these reactions and to develop catalysts.This Account describes our recent investigations on catalytic HER, OER, and ORR with metalloporphyrins and derivatives. Metalloporphyrins are used in nature for light harvesting, energy conversion, electron transfer, O2 activation, and peroxide degradation. Synthetic metal porphyrin complexes are shown to be active for these reactions. We focused on exploring metalloporphyrins to study reaction mechanisms and structure-function relationships because they have stable and tunable structures and characteristic spectroscopic properties.For HER, we identified three H-H bond formation mechanisms and established the correlation between these processes and metal hydride electronic structures. Importantly, we provided direct experimental evidence for the bimetallic homolytic H-H bond formation mechanism by using sterically bulky porphyrins. Homolytic HER has been long proposed but rarely verified because the coupling of active hydride intermediates occurs spontaneously and quickly, making their detection challenging. By blocking the bimolecular mechanism through steric effects, we stabilized and characterized the NiIII-H intermediate and verified homolytic HER by comparing the reaction behaviors of Ni porphyrins with and without steric effects. We therefore provided an unprecedented example to control homolytic versus heterolytic HER mechanisms through tuning steric effects of molecular catalysts.For the OER, the water nucleophilic attack (WNA) on high-valent terminal Mn-oxo has been proposed for the O-O bond formation in natural and artificial water oxidation. By using Mn tris(pentafluorophenyl)corrole, we identified MnV(O) and MnIV-peroxo intermediates in chemical and electrochemical OER and provided direct experimental evidence for the Mn-based WNA mechanism. Moreover, we demonstrated several catalyst design strategies to enhance the WNA rate, including the pioneering use of protective axial ligands. By studying Cu porphyrins, we proposed a bimolecular coupling mechanism between two metal-hydroxide radicals to form O-O bonds. Note that late-transition metals do not likely form terminal metal-oxo/oxyl.For the ORR, we presented several strategies to improve activity and selectivity, including providing rapid electron transfer, using electron-donating axial ligands, introducing hydrogen-bonding interactions, constructing dinuclear cooperation, and employing porphyrin-support domino catalysis. Importantly, we used Co porphyrin atropisomers to realize both two-electron and four-electron ORR, representing an unparalleled example to control ORR selectivity by tuning only steric effects without modifying molecular and/or electronic structures.Lastly, we developed several strategies to graft metalloporphyrins on various electrode materials through different covalent bonds. The molecular-engineered materials exhibit boosted electrocatalytic performance, highlighting promising applications of molecular electrocatalysis. Taken together, this Account demonstrates the benefits of exploring metalloporphyrins for the HER, OER, and ORR. The knowledge learned herein is valuable for the development of porphyrin-based catalysts and also other molecular and material catalysts for small molecule activation reactions.

Introducing Water-Network-Assisted Proton Transfer for Boosted Electrocatalytic Hydrogen Evolution with Cobalt Corrole.

Proton transfer is vital for many biological and chemical reactions. Hydrogen-bonded water-containing networks are often found in enzymes to assist proton transfer, but similar strategy has been rarely presented by synthetic catalysts. We herein report the Co corrole 1 with an appended crown ether unit and its boosted activity for the hydrogen evolution reaction (HER). Crystallographic and 1 H NMR studies proved that the crown ether of 1 can grab water via hydrogen bonds. By using protic acids as proton sources, the HER activity of 1 was largely boosted with added water, while the activity of crown-ether-free analogues showed very small enhancement. Inhibition studies by adding 1) external 18-crown-6-ether to extract water molecules and 2) potassium ion or N-benzyl-n-butylamine to block the crown ether of 1 further confirmed its critical role in assisting proton transfer via grabbed water molecules. This work presents a synthetic example to boost HER through water-containing networks.

Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex.

Water nucleophilic attack (WNA) on high-valent terminal Mn-oxo species is proposed for O-O bond formation in natural and artificial water oxidation. Herein, we report an electrocatalytic water oxidation reaction with MnIII tris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O2 was generated at the MnV/IV potential with hydroxide, but a more anodic potential was required to evolve O2 with only water. With a synthetic MnV(O) complex of 1, a second-order rate constant, k2(OH-), of 7.4 × 103 M-1 s-1 was determined in the reaction of the MnV(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with a k2(H2O) value of 4.4 × 10-3 M-1 s-1. This large reactivity difference of MnV(O) with hydroxide and water is consistent with different electrocatalytic behaviors of 1 with these two substrates. Significantly, during the electrolysis of 1 with water, a MnIV-peroxo species was identified with various spectroscopic methods, including UV-vis, electron paramagnetic resonance, and infrared spectroscopy. Isotope-labeling experiments confirmed that both O atoms of this peroxo species are derived from water, suggesting the involvement of the WNA mechanism in water oxidation by a Mn complex. Density functional theory calculations suggested that the nucleophilic attack of hydroxide on MnV(O) and also WNA to 1e--oxidized MnV(O) are feasibly involved in the catalytic cycles but that direct WNA to MnV(O) is not likely to be the main O-O bond formation pathway in the electrocatalytic water oxidation by 1.

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 αßαß and αααα catalyze ORR with n=2.10 and 3.75 (n is the electron number transferred per O2 ), respectively, but ααßß and αααß show poor selectivity with n=2.89-3.10. Isomer αßαß 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.

Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect.

Several H-H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e-reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2 . Understanding HER processes, especially controllable switching between homolytic and heterolytic H-H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.

Molecular Engineering of a 3D Self-Supported Electrode for Oxygen Electrocatalysis in Neutral Media.

Electrodes for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are required in energy conversion and storage technologies. An assembly strategy involves covalently grafting Co corrole 1 onto Fe3 O4 nanoarrays grown on Ti mesh. The resulted electrode shows significantly improved activity and durability for OER and ORR in neutral media as compared to Fe3 O4 alone and with directly adsorbed 1. It also displays higher atom efficiency (at least two magnitudes larger turnover frequency) than reported electrodes. Using this electrode in a neutral Zn-air battery, a small charge-discharge voltage gap of 1.19 V, large peak power density of 90.4 mW cm-2 , and high rechargeable stability for >100 h are achieved, opening a promising avenue of molecular electrocatalysis in a metal-air battery. This work shows a molecule-engineered electrode for electrocatalysis and demonstrates their potential applications in energy conversion and storage.

Convenient Immobilization of Cobalt Corroles on Carbon Nanotubes through Covalent Bonds for Electrocatalytic Hydrogen and Oxygen Evolution Reactions.

Two different methods were used to immobilize Co corroles on carbon nanotubes (CNTs) through covalent bonds. The resulting CNTs engineered with Co corroles were used as electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in aqueous solutions of pH 0, 7, and 14. For both HER and OER in all solutions, the hybrids obtained by attaching Co corroles on CNTs through amidation coupling showed better performance. This is likely because the large surface area and good electrical conductivity of CNTs can be well preserved during the amidation reaction under mild conditions.

Carbon Nanotubes with Cobalt Corroles for Hydrogen and Oxygen Evolution in pH†0-14 Solutions.

Water splitting is promising to realize a hydrogen-based society. The practical use of molecular water-splitting catalysts relies on their integration onto electrode materials. We describe herein the immobilization of cobalt corroles on carbon nanotubes (CNTs) by four strategies and compare the performance of the resulting hybrids for H2 and O2 evolution. Co corroles can be covalently attached to CNTs with short conjugated linkers (the hybrid is denoted as H1) or with long alkane chains (H2), or can be grafted to CNTs via strong π-π interactions (H3) or via simple adsorption (H4). An activity trend H1≫H3>H2≈H4 is obtained for H2 and O2 evolution, showing the critical role of electron transfer ability on electrocatalysis. Notably, H1 is the first Janus catalyst for both H2 and O2 evolution reactions in pH 0-14 aqueous solutions. Therefore, this work is significant to show potential uses of electrode materials with well-designed molecular catalysts in electrocatalysis.

Selective visible-light-driven oxygen reduction to hydrogen peroxide using BODIPY photosensitizers.

Selective visible-light-driven O2 reduction to H2O2 was realized using BODIPY photosensitizers (PS) in the presence of ferrocene (Fc) as the reductant and acetic acid as the proton source. Mechanistic studies suggested that O2 could be activated by 3PS* through an energy transfer pathway to give singlet oxygen (1O2) in the absence of Fc. However, with Fc, 3PS* was first reductively quenched to PS˙-, which was able to reduce O2 to the superoxide radical form in a subsequent electron transfer step.

Graphene-Supported Pyrene-Modified Cobalt Corrole with Axial Triphenylphosphine for Enhanced Hydrogen Evolution in pH†0-14 Aqueous Solutions.

A cobalt complex of 5,15-bis(pentafluorophenyl)-10-(4)-(1-pyrenyl)phenyl corrole that contains a triphenylphosphine axial ligand (1-PPh3 ) was synthesized and examined as an electrocatalyst for the hydrogen evolution reaction (HER). If supported on graphene (G), the resulting 1-PPh3 /G material can catalyze the HER in aqueous solutions over a wide pH range of 0-14 with a high efficiency and durability. The significantly enhanced activity of 1-PPh3 /G, compared with that of its analogues 1-py/G (the Co-bound axial ligand is pyridine instead of triphenylphosphine) and 2-py/G (Co complex of 5,10,15-tris(pentafluorophenyl)corrole), highlights the effects of the pyrenyl substituent and the triphenylphosphine axial ligand on the HER activity. On one hand, the pyrenyl moiety can increase the π-π interactions between 1 and graphene and thus lead to a fast electron transfer from the electrode to 1. On the other hand, the triphenylphosphine axial ligand can increase the electron density (basicity) of Co and thus make the metal center more reactive to protons at the trans position through a so-called "push effect". This study concerns a significant example that shows the trans effect of the axial ligand on the HER, which has been investigated rarely. The combination of various ligand-design strategies in one molecule has been realized in 1-PPh3 to achieve a high catalytic HER performance. These factors are valuable to be used in other molecular catalyst systems.

[Clinic analysis of 16 patients of craniocerebral trauma with Labbé vein injury].

OBJECTIVES: To study the mechanism of Labbé vein injury, and its effect on traumatic cerebral infarction and prognosis in patients of craniocerebral trauma. METHODS: The clinic imageology and data of 16 patients of craniocerebral trauma with Labbé vein injury approved intraoperatively from June 2006 to February 2009 were analyzed. To compare the effect of the intraoperative finding of Labbé vein damage and blood vessel treatment on traumatic cerebral infarction, and to analyze the traumatic cerebral infarction size and prognosis. RESULTS: All the 16 patients had acute subdural hematoma and(or) intracerebral hematoma. And 15 of all the 16 patients with Labbé vein injury suffered from skull fractures. All patients accepted hematoma cleaning and intracranial decompression procedure by removing skull. The preoperative Glasgow coma scale (GCS) were as following: 5 patients being between 9 - 12, 7 patients being between 6 - 8 and 4 patients being between 3 - 5. Eight patients had cerebral hernia before operations on admission, and among them, 3 patients had corectasis of both sides and 5 patients had corectasis of only one side, the other 8 patients had no corectasis. Postoperatively, 14 patients suffered from traumatic cerebral infarction of different grades. After follow-ups of 24 months, 8 patients had relatively good prognosis, with 4 patients having good recoveries and 4 having middle disability; the other 8 had bad prognosis, including 3 patients being seriously disable and 5 kept vegetative state. CONCLUSIONS: Impact injury and counterblow are the main reasons to the injury of Labbé vein, which consequently leads to serious traumatic cerebral infarction and bad prognosis. Intraoperatively, it is quite important to protect Labbé vein during the surgery, which should not be easily cut or obstructed by electric coagulation, and this is an effective way to improve the prognosis of these patients.