Proton-coupled Electron Transfer Process Research Articles

Bridging Nickel-MOF and Copper Single Atoms/Clusters with H-Substituted Graphdiyne for the Tandem Catalysis of Nitrate to Ammonia.

Interfacial engineering of synergistic catalysts is one of the keys to achieving multiple proton-coupled electron transfer processes in nitrate-to-ammonia conversion. Herein, by joining ultrathin nickel-based metal-organic framework (denoted Ni-MOF) nanosheets with few-layered hydrogen-substituted graphdiyne-supported copper single atoms and clusters (denoted HsGDY@Cu), a tandem catalyst of Ni-MOFs@HsGDY@Cu with dual-active interfaces was developed for the concerted catalysis of nitrate-to-ammonia. In such a system, the sandwiched HsGDY layer could serve as a bridge to connect the coordinated unsaturated Ni2+ sites with Cu single atoms/clusters in a limited range of 0 to 3.6 nm. From Ni2+ to Cu, via the hydrogen spillover process, the hydrogen radicals (H⋅) generated at the unsaturated Ni2+ sites could migrate across HsGDY to the Cu sites to participate in the transformation of *HNO3 to NH3. From Cu to Ni2+, bypassing the higher reaction energy for *HNO3 formation on the Ni2+ sites, the NO2 - detached from the Cu sites could diffuse onto the unsaturated Ni2+ sites to form NH3 as well. The combined results make this hybrid a tandem catalyst with dual active sites for the catalysis of nitrate-to-ammonia conversion with improved Faradaic efficiency at lower overpotentials.

Visible light-driven molecular oxygen activation by lead-zinc smelting slag and tartaric acid for efficient organic pollutant degradation and Cr(VI) reduction

The remediation of heavy metal and organic-contaminated wastewater remains a significant concern in environmental science, necessitating the development of cost-effective and efficient treatment systems. This study focuses on the setup of a highly effective molecular oxygen (O2) activation system using lead–zinc smelting slag (LZSS) and tartaric acid (TA) under visible light. The LZSS-TA complex exhibited rapid photochemical reactions and demonstrated a remarkable capacity for O2 activation, resulting in the in situ generation of hydrogen peroxide (H2O2) and 99 % degradation of para-chloroaniline (p-CA). The formation of H2O2 occurred through a two-step single electron transfer pathway, whereby C-centered radicals (CHOHCHOHCOO−) generated within the system initiated the reduction of O2 to form O2−, as a crucial intermediate. The produced O2− is then reduced by Fe(II) to generate H2O2 via proton-coupled electron transfer (PCET) processes. Light-induced ligand-to-metal charge transfer (LMCT) process is the key to the production of C-centered radicals and Fe(II), which determines the production efficiency of H2O2 and OH. Additionally, this system enabled simultaneous oxidation of p-CA by 98 % and reduction of Cr(VI) by 100 % within 60 min. More importantly, O2 activation by TA-assisted LZSS under natural sunlight/solar irradiation could efficiently degrade p-CA in both ultrapure water (94 %) and reservoir water (92.5 %) within 210 min. This study significantly contributes to the understanding of light-driven O2 activation and lays the foundation for the design of cost-effective and efficient pollution remediation systems.

Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water.

A new cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3'-Co(8,9,12-Cl3-1,2-C2B9H8)2]2, 5, has been synthesized and fully characterized for the first time. In this system, the photoredox catalyst [3,3'-Co(8,9,12-Cl3-1,2-C2B9H8)2]-[Cl6-1]-, a metallacarborane, and the oxidation catalyst [RuII(trpy)(bpy)(H2O)]2+, 2 are linked by non-covalent interactions. This compound, along with the one previously synthesized by us, [RuII(trpy)(bpy)(H2O)][(3,3'-Co(1,2-C2B9H11)2]2, 4, are the only examples of cooperative molecular photocatalysts in which the catalyst and photosensitizer are not linked by covalent bonds. Both cooperative systems have proven to be efficient photocatalysts for the oxidation of alkenes in water through Proton Coupled Electron Transfer processes (PCETs). Using 0.05 mol% of catalyst 4, total conversion values were achieved after 15 min with moderate selectivity for the corresponding epoxides, which decreases with reaction time, along with the TON values. However, with 0.005 mol% of catalyst, the conversion values are lower, but the selectivity and TON values are higher. This occurs simultaneously with an increase in the amount of the corresponding diol for most of the substrates studied. Photocatalyst 4 acts as a photocatalyst in both the epoxidation of alkenes and their hydroxylation in aqueous medium. The hybrid system 5 shows generally higher conversion values at low loads compared to those obtained with 4 for most of the substrates studied. However, the selectivity values for the corresponding epoxides are lower even after 15 min of reaction. This is likely due to the enhanced oxidizing capacity of CoIV in catalyst 5, resulting from the presence of more electron-withdrawing substituents on the metallacarborane platform.

Synthesis of graphitic carbon nitride (g-C3N4) by high-temperature condensation for electrochemical evaluation of dichlorophen and thymol in environmental trials

The work deals with synthesizing carbon-based nanomaterial, i.e., graphitic carbon nitride, which was carried out using the high-temperature condensation method. Graphitic carbon nitride is characterized by cost efficiency, increased thermal resilience, a two-dimensional molecular layer structure, biocompatibility and stability. These properties can be used in the electrochemical investigations of fungicides such as dichlorophen and thymol. The synthesized nanomaterial was first characterized using XRD, SEM, UV-DRS, BET, FTIR, CV and EIS investigations. The cyclic voltammetry behavior of dichlorophen and thymol shows the proton-coupled irreversible electron transfer process at a modified carbon paste electrode with the participation of same number of protons and electrons. The developed sensor exhibited good detection limits for the dichlorophen and thymol as low as 15.3 nM and 12.0 nM with the sensitivity of 126.8 µA·µM−1·cm−2 and 59.2 µA·µM−1·cm−2, respectively. The applicability of the developed sensor was tested in spiked soil and water samples, and good recoveries were achieved with a% RSD of 1.67 and 1.30, respectively. The anti-interference responses to metal ions demonstrate the selectivity (qualitative) of the developed sensor in the electrochemical detection of dichlorophen and thymol. In the future, the sensor developed would offer the potential to sensitively and selectively detect other pesticide molecules in environmental samples.

Efficient Proton Transfer and Charge Separation within Covalent Organic Frameworks via Hydrogen-Bonding Network to Boost H2O2 Photosynthesis.

Photocatalytic synthesis based on the oxygen reduction reaction (ORR) has shown great promise for H2O2 production. However, the low activity and selectivity of 2e- ORR result in a fairly low efficiency of H2O2 production. Herein, we propose a strategy to enhance the proton-coupled electron transfer (PCET) process in covalent organic frameworks (COFs), thereby significantly boosting H2O2 photosynthesis. We demonstrated that the construction of a hydrogen-bonding network, achieved by anchoring the H3PO4 molecular network on COF nanochannels, can greatly improve both proton conductivity and photogenerated charge separation efficiency of COFs. Thus, COF@H3PO4 exhibited superior photocatalytic performance in generating H2O2 without sacrificial agents, with a solar-to-chemical conversion efficiency as high as 0.69%. Results indicated that a much more localized spatial distribution of energy band charge density on COF@H3PO4 led to efficient charge separation, and the small energy barrier of the rate-limiting step from *OOH to H2O2 endowed COF@H3PO4 with higher 2e- ORR selectivity.

Replacing a Cysteine Ligand by Selenocysteine in a [NiFe]-Hydrogenase Unlocks Hydrogen Production Activity and Addresses the Role of Concerted Proton-Coupled Electron Transfer in Electrocatalytic Reversibility.

Hydrogenases catalyze hydrogen/proton interconversion that is normally electrochemically reversible (having minimal overpotential requirement), a special property otherwise almost exclusive to platinum metals. The mechanism of [NiFe]-hydrogenases includes a long-range proton-coupled electron-transfer process involving a specific Ni-coordinated cysteine and the carboxylate of a nearby glutamate. A variant in which this cysteine has been exchanged for selenocysteine displays two distinct changes in electrocatalytic properties, as determined by protein film voltammetry. First, proton reduction, even in the presence of H2 (a strong product inhibitor), is greatly enhanced relative to H2 oxidation: this result parallels a characteristic of natural [NiFeSe]-hydrogenases which are superior H2 production catalysts. Second, an inflection (an S-shaped "twist" in the trace) appears around the formal potential, the small overpotentials introduced in each direction (oxidation and reduction) signaling a departure from electrocatalytic reversibility. Concerted proton-electron transfer offers a lower energy pathway compared to stepwise transfers. Given the much lower proton affinity of Se compared to that of S, the inflection provides compelling evidence that concerted proton-electron transfer is important in determining why [NiFe]-hydrogenases are reversible electrocatalysts.

Bioinspired Water Preorganization in Confined Space for Efficient Water Oxidation Catalysis in Metallosupramolecular Ruthenium Architectures.

ConspectusNature has established a sustainable way to maintain aerobic life on earth by inventing one of the most sophisticated biological processes, namely, natural photosynthesis, which delivers us with organic matter and molecular oxygen derived from the two abundant resources sunlight and water. The thermodynamically demanding photosynthetic water splitting is catalyzed by the oxygen-evolving complex in photosystem II (OEC-PSII), which comprises a distorted tetramanganese-calcium cluster (CaMn4O5) as catalytic core. As an ubiquitous concept for fine-tuning and regulating the reactivity of the active site of metalloenzymes, the surrounding protein domain creates a sophisticated environment that promotes substrate preorganization through secondary, noncovalent interactions such as hydrogen bonding or electrostatic interactions. Based on the high-resolution X-ray structure of PSII, several water channels were identified near the active site, which are filled with extensive hydrogen-bonding networks of preorganized water molecules, connecting the OEC with the protein surface. As an integral part of the outer coordination sphere of natural metalloenzymes, these channels control the substrate and product delivery, carefully regulate the proton flow by promoting pivotal proton-coupled electron transfer processes, and simultaneously stabilize short-lived oxidized intermediates, thus highlighting the importance of an ordered water network for the remarkable efficiency of the natural OEC.Transferring this concept from nature to the engineering of artificial metal catalysts for fuel production has fostered the fascinating field of metallosupramolecular chemistry by generating defined cavities that conceptually mimic enzymatic pockets. However, the application of supramolecular approaches to generate artificial water oxidation catalysts remained scarce prior to our initial reports, since such molecular design strategies for efficient activation of substrate water molecules in confined nanoenvironments were lacking. In this Account, we describe our research efforts on combining the state-of-the art Ru(bda) catalytic framework with structurally programmed ditopic ligands to guide the water oxidation process in defined metallosupramolecular assemblies in spatial proximity. We will elucidate the governing factors that control the quality of hydrogen-bonding water networks in multinuclear cavities of varying sizes and geometries to obtain high-performance, state-of-the-art water oxidation catalysts. Pushing the boundaries of artificial catalyst design, embedding a single catalytic Ru center into a well-defined molecular pocket enabled sophisticated water preorganization in front of the active site through an encoded basic recognition site, resulting in high catalytic rates comparable to those of the natural counterpart OEC-PSII.To fully explore their potential for solar fuel devices, the suitability of our metallosupramolecular assemblies was demonstrated under (electro)chemical and photocatalytic water oxidation conditions. In addition, testing the limits of structural diversity allowed the fabrication of self-assembled linear coordination oligomers as novel photocatalytic materials and long-range ordered covalent organic framework (COF) materials as recyclable and long-term stable solid-state materials for future applications.

Transition-Metal Porphyrin-Based MOFs In Situ-Derived Hybrid Catalysts for Electrocatalytic CO2 Reduction.

Excellent electrocatalytic CO2 reduction reaction activity has been demonstrated by transition metals and nitrogen-codoped carbon (M-N-C) catalysts, especially for transition-metal porphyrin (MTPP)-based catalysts. In this work, we propose to use one-step low-temperature pyrolysis of the isostructural MTPP-based metal-organic frameworks (MOFs) and electrochemical in situ reduction strategies to obtain a series of hybrid catalysts of Co nanoparticles (Co NPs) and MTPP, named Co NPs/MTPP (M = Fe, Co, and Ni). The in situ introduction of Co NPs can efficiently enhance the electrocatalytic ability of MTPP (M = Fe, Co, and Ni) to convert CO2 to CO, particularly for FeTPP. Co NPs/FeTPP endowed a high CO faradaic efficiency (FECOmax = 95.5%) in the H cell, and the FECO > 90.0% is in the broad potential range of -0.72 to -1.22 VRHE. In addition, the Co NPs/FeTPP achieved 145.4 mA cm-2 at a lower potential of -0.70 VRHE with an FECO of 94.7%, and the CO partial currents increased quickly to reach 202.2 mA cm-2 at -0.80 VRHE with an FECO of 91.6% in the flow cell. It is confirmed that Co NPs are necessary for hybrid catalysts to get superior electrocatalytic activity; Co NPs also can accelerate H2O dissociation and boost the proton supply capacity to hasten the proton-coupled electron-transfer process, effectively adjusting the adsorption strength of the reaction intermediates.

2,2'-Bipyridine-Enabled Photocatalytic Radical [4+2] Cyclization of N-Aryl-α-amino Acids for Synthesizing Polysubstituted Tetrahydroquinolines.

A facile photocatalytic radical [4+2] cyclization of N-aryl-α-amino acids with various alkenes to access structurally polysubstituted tetrahydroquinolines has been developed. Using a simple bipyridine as a catalyst, different N-aryl-α-amino acids could be utilized as the radical precursors to react with diverse electrophilic alkenes, including exocyclic terminal alkenes, acyclic terminal alkenes, and cycloalkenes, producing 10 types of nitrogen-containing heterocyclic compounds fused in multiple frameworks in generally moderate yields with good diastereoselectivities. Scale-up synthesis and transformations of the products further demonstrated the synthetic application of this protocol. Moreover, a decarboxylative radial pathway via a proton-coupled electron transfer process for illustration of this [4+2] cyclization was proposed on the basis of the control experiments. This process is highlighted by a simple bipyridine photocatalysis, mild reaction conditions, various N-aryl-α-amino acids and alkene materials, and application for the modification of natural products.

Anthraquinone-based polymer modified BiVO4 photoanode with strong electron-withdrawing functional groups for boasting photoelectrochemical water oxidation

The photoelectrochemical (PEC) performance ofBiVO4 is limited by sluggish water oxidation kinetics and severe carrier recombination. Herein, a novel high-performance BiVO4/NiFe-NOAQ photoanode is prepared by a simple one-step hydrothermal method, using BiVO4 and 1-Nitroanthraquinone (NOAQ) as raw materials. The BiVO4/NiFe-NOAQ photoanode has an excellent photocurrent density of 5.675 mA cm−2 at 1.23 VRHE, which is 3.35 times higher than that of the pure BiVO4 (1.693 mA cm−2) photoanode. The BiVO4/NiFe-NOAQ shows a significant improvement in charge separation efficiency (86.12 %) and charge injection efficiency (87.86 %). The improvement is ascribable to the NiFe-NOAQ form a type II heterojunction with BiVO4 to inhibit carrier recombination. More importantly, the kinetic isotope experiment suggests that the proton-coupled electron transfer (PCET) process can enhance the charge transfer of BiVO4/NiFe-NOAQ. The contact angle measurements show that modifying functional groups enhanced the hydrophilicity of BiVO4/NiFe-NOAQ, which can further accelerate the PCET process. The XPS and PL results as well as the tauc plot indicate that the strong electron-withdrawing ability of –NO2 which can promote the extension of π conjugation, results in more π electron delocalization and produces more efficient active sites, thus achieving efficient photoelectrochemical water oxidation.

Unraveling a Concerted Proton-Coupled Electron Transfer Pathway in Atomically Precise Gold Nanoclusters.

Metal nanoclusters (MNCs) represent a promising class of materials for catalytic carbon dioxide and proton reduction as well as dihydrogen oxidation. In such reactions, multiple proton-coupled electron transfer (PCET) processes are typically involved, and the current understanding of PCET mechanisms in MNCs has primarily focused on the sequential transfer mode. However, a concerted transfer pathway, i.e., concerted electron-proton transfer (CEPT), despite its potential for a higher catalytic rate and lower reaction barrier, still lacks comprehensive elucidation. Herein, we introduce an experimental paradigm to test the feasibility of the CEPT process in MNCs, by employing Au18(SR)14 (SR denotes thiolate ligand), Au22(SR)18, and Au25(SR)18- as model clusters. Detailed investigations indicate that the photoinduced PCET reactions in the designed system proceed via an CEPT pathway. Furthermore, the rate constants of gold nanoclusters (AuNCs) have been found to be correlated with both the size of the cluster and the flexibility of the Au-S framework. This newly identified PCET behavior in AuNCs is prominently different from that observed in semiconductor quantum dots and plasmonic metal nanoparticles. Our findings are of crucial importance for unveiling the catalytic mechanisms of quantum-confined metal nanomaterials and for the future rational design of more efficient catalysts.

Activation of Ga Liquid Catalyst with Continuously Exposed Active Sites for Electrocatalytic C-N Coupling.

Environmentally friendly electrocatalytic coupling of CO2 and N2 for urea synthesis is a promising strategy. However, it is still facing problems such as low yield as well as low stability. Here, a new carbon-coated liquid alloy catalyst, Ga79 Cu11 Mo10 @C is designed for efficient electrochemical urea synthesis by activating Ga active sites. During the N2 and CO2 co-reduction process, the yield of urea reaches 28.25 mmol h-1 g-1 , which is the highest yield reported so far under the same conditions, the Faraday efficiency (FE) is also as high as 60.6 % at -0.4 V vs. RHE. In addition, the catalyst shows excellent stability under 100 h of testing. Comprehensive analyses showed that sequential exposure of a high density of active sites promoted the adsorption and activation of N2 and CO2 for efficient coupling reactions. This coupling reaction occurs through a thermodynamic spontaneous reaction between *N=N* and CO to form a C-N bond. The deformability of the liquid state facilitates catalyst recovery and enhances stability and resistance to poisoning. Moreover, the introduction of Cu and Mo stimulates the Ga active sites, which successfully synthesises the *NCON* intermediate. The reaction energy barrier of the third proton-coupled electron transfer process rate-determining step (RDS) *NHCONH→*NHCONH2 was lowered, ensuring the efficient synthesis of urea.

Electrokinetic Analyses Uncover the Rate‐Determining Step of Biomass‐Derived Monosaccharide Electroreduction on Copper

AbstractElectrochemical biomass conversion holds promise to upcycle carbon sources and produce valuable products while reducing greenhouse gas emissions. To this end, deep insight into the interfacial mechanism is essential for the rational design of an efficient electrocatalytic route, which is still an area of active research and development. Herein, we report the reduction of dihydroxyacetone (DHA)—the simplest monosaccharide derived from glycerol feedstock—to acetol, the vital chemical intermediate in industries, with faradaic efficiency of 85±5 % on a polycrystalline Cu electrode. DHA reduction follows preceding dehydration by coordination with the carbonyl and hydroxyl groups and the subsequent hydrogenation. The electrokinetic profile indicates that the rate‐determining step (RDS) includes a proton‐coupled electron transfer (PCET) to the dehydrated intermediate, revealed by coverage‐dependent Tafel slope and isotopic labeling experiments. An approximate zero‐order dependence of H+ suggests that water acts as the proton donor for the interfacial PCET process. Leveraging these insights, we formulate microkinetic models to illustrate its origin that Eley–Rideal (E−R) dominates over Langmuir–Hinshelwood (L−H) in governing Cu‐mediated DHA reduction, offering rational guidance that increasing the concentration of the adsorbed reactant alone would be sufficient to promote the activity in designing practical catalysts.

Electrokinetic Analyses Uncover the Rate-Determining Step of Biomass-Derived Monosaccharide Electroreduction on Copper.

Electrochemical biomass conversion holds promise to upcycle carbon sources and produce valuable products while reducing greenhouse gas emissions. To this end, deep insight into the interfacial mechanism is essential for the rational design of an efficient electrocatalytic route, which is still an area of active research and development. Herein, we report the reduction of dihydroxyacetone (DHA)-the simplest monosaccharide derived from glycerol feedstock-to acetol, the vital chemical intermediate in industries, with faradaic efficiency of 85±5 % on a polycrystalline Cu electrode. DHA reduction follows preceding dehydration by coordination with the carbonyl and hydroxyl groups and the subsequent hydrogenation. The electrokinetic profile indicates that the rate-determining step (RDS) includes a proton-coupled electron transfer (PCET) to the dehydrated intermediate, revealed by coverage-dependent Tafel slope and isotopic labeling experiments. An approximate zero-order dependence of H+ suggests that water acts as the proton donor for the interfacial PCET process. Leveraging these insights, we formulate microkinetic models to illustrate its origin that Eley-Rideal (E-R) dominates over Langmuir-Hinshelwood (L-H) in governing Cu-mediated DHA reduction, offering rational guidance that increasing the concentration of the adsorbed reactant alone would be sufficient to promote the activity in designing practical catalysts.

Metal-Free Activation of Molecular Oxygen by Quaternary Ammonium-Based Ionic Liquid: A Detail Mechanistic Study.

Most oxidation processes in common organic synthesis and chemical biology require transition metal catalysts or metalloenzymes. Herein, we report a detailed mechanistic study of a metal-free oxygen (O2) activation protocol on benzylamine/alcohols using simple quaternary alkylammonium-based ionic liquids to produce products such as amide, aldehyde, imine, and in some cases, even aromatized products. NMR and various control experiments established the product formation and reaction mechanism, which involved the conversion of molecular oxygen into a hydroperoxyl radical via a proton-coupled electron transfer process. Detection of hydrogen peroxide in the reaction medium using colorimetric analysis supported the proposed mechanism of oxygen activation. Furthermore, first-principles calculations using density functional theory (DFT) revealed that reaction coordinates and transition state spin densities have a unique spin conversion of triplet oxygen leading to formation of singlet products via a minimum energy crossing point. In addition to DFT, domain-based local pair natural orbital coupled cluster, (DLPNO-CCSD(T)), and complete active space self-consistent field, CASSCF(20,14) methods complemented the above findings. Partial density of states analysis showed stabilization of π* orbital of oxygen in the presence of ionic liquid, making it susceptible to hydrogen abstraction in a mild, metal-free condition. Inductively coupled plasma atomic emission spectroscopic (ICP-AES) analysis of reactant and ionic liquids clearly showed the absence of any significant transition metal contamination. The current results described the origin of O2 activation within the context of molecular orbital (MO) theory and opened up a new avenue for the use of ionic liquids as inexpensive, multifunctional and high-performance alternative to metal-based catalysts for O2 activation.

Matched Redox Kinetics on Triazine-Based Carbon Nitride/Ni(OH)2 for Stoichiometric Overall Photocatalytic CO2 Conversion.

Mismatched reaction kinetics of CO2 reduction and H2 O oxidation is the main obstacle limiting the overall photocatalytic CO2 conversion. Here, a molten salt strategy is used to construct tubular triazine-based carbon nitride (TCN) with more adsorption sites and stronger activation capability. Ni(OH)2 nanosheets are then grown over the TCN to trigger a proton-coupled electron transfer for a stoichiometric overall photocatalytic CO2 conversion via "3CO2 + 2H2 O = CH4 + 2CO + 3O2 ." TCN reduces the energy barrier of H2 O dissociation to promote H2 O oxidation to O2 and supply sufficient protons to Ni(OH)2 , whereby the CO2 conversion is accelerated due to the enhanced proton-coupled electron transfer process enabled by the sufficient proton supply from TCN. This work highlights the importance of matching the reaction kinetics of CO2 reduction and H2 O oxidation by proton-coupled electron transfer on stoichiometric overall photocatalytic CO2 conversion.

Coordination-induced O-H/N-H bond weakening by a redox non-innocent, aluminum-containing radical

Several renewable energy schemes aim to use the chemical bonds in abundant molecules like water and ammonia as energy reservoirs. Because the O-H and N-H bonds are quite strong (>100 kcal/mol), it is necessary to identify substances that dramatically weaken these bonds to facilitate proton-coupled electron transfer processes required for energy conversion. Usually this is accomplished through coordination-induced bond weakening by redox-active metals. However, coordination-induced bond weakening is difficult with earth’s most abundant metal, aluminum, because of its redox inertness under mild conditions. Here, we report a system that uses aluminum with a redox non-innocent ligand to achieve significant levels of coordination-induced bond weakening of O-H and N-H bonds. The multisite proton-coupled electron transfer manifold described here points to redox non-innocent ligands as a design element to open coordination-induced bond weakening chemistry to more elements in the periodic table.

Photocatalytic Synthesis of Indanone, Pyrone, and Pyridinone Derivatives with Diazo Compounds as Radical Precursors.

We disclose herein a photocatalytic radical cascade cyclization of diazoalkanes for the divergent synthesis of important carbocycles and heterocycles. Under the optimal reaction conditions, various indanone, pyrone, and pyridinone derivatives can be obtained in moderate to good yields. Mechanistic experiments support the formation of carbon-centered radicals from diazoalkanes through the proton-coupled electron transfer process. Scale-up reaction using continuous flow technology and useful downstream application of the formed heterocycles further render the strategy attractive and valuable.

Additive-controlled chemoselective inter-/intramolecular hydroamination via electrochemical PCET process.

Electrochemically generated amidyl radical species produced distinct inter- or intramolecular hydroamination reaction products via a proton-coupled electron transfer (PCET) mechanism. Cyclic voltammetry (CV) analysis indicated that the chemoselectivity was derived from the size of the hydrogen bond complex, which consisted of the carbamate substrate and phosphate base, and could be controlled using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as an additive. These results provide fundamental insights for the design of PCET-based redox reaction systems under electrochemical conditions.

Photocatalytic Conversion of Lignin Models into Functionalized Aromatic Molecules Initiated by the Proton-Coupled Electron Transfer Process.

A mild and efficient method for lignin β-O-4 cleavage and functionalization was achieved via photocatalysis. This protocol exhibits a broad scope of lignin models and excellent compatibility of functionalization reagents, constructing a series of functionalized lignin-based aromatic compounds. Highly selective formation of alkyl radical species through a proton-coupled electron transfer and β-scission process provides the opportunity to form new C-C and C-N bonds by reaction with electrophilic reagents.