Electron Oxygen Reduction Reaction Research Articles

A quaternary ammonium cyclodextrin polymer for efficient photocatalytic production of hydrogen peroxide from pure water

A photocatalytic system can be used to efficiently produce hydrogen peroxide (H2O2) without introducing a sacrificial agent or oxygen (O2). This system has practical application potential but remains challenging to implement. To increase the H2O2 yield of this system, a quaternary ammonium cyclodextrin polymeric photocatalyst QCD36A1-1350 is successfully synthesized using quaternization modification and low-temperature polycondensation. The photocatalyst is used to produce H2O2 from pure water and air by the one-step two electron oxygen reduction reaction. Under irradiation by visible light, QCD36A1-1350 produces a higher H2O2 yield (of up to 2.51 mmol g−1h−1) than unquaternized polymers and reported metal-free catalysts under similar conditions. Experimental and theoretical studies clearly show that the introduction of quaternary ammonium groups can effectively broaden the visible light absorption of polymer catalysts, while increasing the hydrophilicity, charge transfer efficiency and surface stability. The practicability of efficient photocatalytic production of H2O2 is realized by increasing the activity and selectivity of the polymer photocatalyst.

Mechanistic Insights into Surfactant-Modulated Electrode-Electrolyte Interface for Steering H2O2 Electrosynthesis.

Electrocatalytic reactions taking place at the electrified electrode-electrolyte interface involve processes of proton-coupled electron transfer. Interfacial protons are delivered to the electrode surface via a H2O-dominated hydrogen-bond network. Less efforts are made to regulate the interfacial proton transfer from the perspective of interfacial hydrogen-bond network. Here, we present quaternary ammonium salt cationic surfactants as electrolyte additives for enhancing the H2O2 selectivity of the oxygen reduction reaction (ORR). Through in situ vibrational spectroscopy and molecular dynamics calculation, it is revealed that the surfactants are irreversibly adsorbed on the electrode surface in response to a given bias potential range, leading to the weakening of the interfacial hydrogen-bond network. This decreases interfacial proton transfer kinetics, particularly at high bias potentials, thus suppressing the 4-electron ORR pathway and achieving a highly selective 2-electron pathway toward H2O2. These results highlight the opportunity for steering H2O-involved electrochemical reactions via modulating the interfacial hydrogen-bond network.

Effective photo-electrochemical production of H2O2 and green Fenton reaction on hierarchical Fe/C/N @ ZIF-8 @ACF for abatement of antibiotics in water

Heterogeneous photo-electro-Fenton (HPEF) reaction is a highly efficient process using H2O2 produced by in-situ two electron oxygen reduction reaction (2e ORR) after aerating for the elimination of refractory organic pollutants. Herein, an effective MOFs derived Fe/C/N @ ZIF-8 @ACF composite electrode for HPEF was prepared by loading Fe/C/N derived from Fe-based metal-organic frameworks (Fe-MOFs) and zeolitic imidazolate framework-8 (ZIF-8) on activated carbon felt (ACF). By supplying air, solar light, and low external electric current (32 mA·cm−2) to the cathode, ZIF-8 could generate H2O2 by 2e- ORR process, and Fe/C/N could react with H2O2 to form strong oxidative radicals (·OH). Photocatalysis accelerates the Fenton reaction greatly with the abundant photo-generated electrons. The HPEF activity of different systems for the degradation of antibiotics was compared. The results showed that the degradation rate of antibiotics can be greatly increased with the best of ∼100% within 100 min. Moreover, the electrode could still maintain a high activity after reuse for 4 times, which proved to be highly active, stable, and well recyclable for a rapid HPEF oxidation for abatement of antibiotic pollutants in water.

Enriched Ti3+ in TiONC electrocatalyst for efficient H2O2 generation via 2-electron oxygen reduction reaction

The 2-electron electrochemical oxygen reduction reaction (ORR) is considered a viable method for synthesizing H2O2 because of its efficiency and environmental friendliness. However, conventional catalysts for this reaction predominantly rely on high-cost metals and require complex preparation procedures. Herein, we synthesized an electrocatalyst containing TiN and N-doped carbon via the pyrolysis of melamine and MIL125(Ti)–NH2. The effects of melamine and pyrolysis temperature on the chemical composition and defect site formation were investigated. Importantly, the obtained results suggest that the generated Ti3+ sites are more important in enhancing the performance of the 2-electron ORR, surpassing defective carbon and oxygen functional groups. In particular, the resulting TiONC-MA-1000 catalyst prepared through pyrolysis at 1,000 °C contained abundant Ti3+ sites, resulting in high 2-electron ORR activity with a molar selectivity exceeding 91 % and high stability over a 12 h testing period. The electrochemical H2O2 generation experiments conducted in an H-cell configuration employing TiONC-MA-1000 as the electrocatalyst yielded 6.99 mol⋅gcatalyst−1⋅h−1 H2O2. Therefore, the present study proposes a facile approach for fabricating highly active electrocatalysts suitable for large-scale H2O2 production.

Engineering Electrode Polarity for Enhancing In Situ Generation of Hydroxyl Radicals Using Granular Activated Carbon

Recently, granular activated carbon (GAC) has shown its effectiveness as a cathode material for in situ ROS generation. Here, we present an electrochemically modified GAC cathode using electrode polarity reversal (PR) approach for enhanced H2O2 decomposition via 2-electron oxygen reduction reaction (2e-ORR). The successful GAC modification using PR necessitates tuning of the operational parameters such as frequency, current, and time intervals between the PR cycles. This modification enhances the GAC hydrophilicity by increasing the density of surface oxygen functionalities. After optimization of the electrode polarity, using the 20 (No PR)-2 (PR) interval and 140 mA current intensity, the •OH concentration reaches 38.9 μM compared to the control (No PR) (28.14 μM). Subsequently, we evaluated the enhanced •OH generation for the removal of glyphosate, a persistent pesticide used as a model contaminant. The modified GAC using PR removed 67.6% of glyphosate compared to 40.6% by the unmodified GAC without PR, respectively. The findings from this study will advance the utilization of GAC for in situ ROS synthesis, which will have direct implications on increasing the effectiveness of electrochemical water treatment systems.

Introduction of electron-deficient unit in resorcinol-formaldehyde resin to construct donor–acceptor conjugated polymer for enhancing photocatalytic H2O2 production

Intramolecular donor–acceptor conjugated polymer was constructed in resorcinol-formaldehyde resin by embedding benzothiadiazole, which can reduce the Gibbs free energy for two-electron oxygen reduction and improve photocatalytic H2O2 evolution.

Dipole-Dipole Tuned Electronic Reconfiguration of Defective Carbon Sites for Efficient Oxygen Reduction into H2 O2.

Metal-free carbon-based materials are one of the most promising electrocatalysts toward 2-electron oxygen reduction reaction (2e-ORR) for on-site production of hydrogen peroxide (H2 O2 ), which however suffer from uncontrollable carbonizations and inferior 2e-ORR selectivity. To this end, a polydopamine (PDA)-modified carbon catalyst with a dipole-dipole enhancement is developed via a calcination-free method. The H2 O2 yield rate outstandingly reaches 1.8mol gcat -1 h-1 with high faradaic efficiency of above 95% under a wide potential range of 0.4-0.7 VRHE , overwhelming most of carbon electrocatalysts. Meanwhile, within a lab-made flow cell, the synthesized ORR electrode features an exceptional stability for over 250h, achieved a pure H2 O2 production efficacy of 306g kWh-1 . By virtue of its industrial-level capabilities, the established flow cell manages to perform a rapid pulp bleaching within 30min. The superior performance and enhanced selectivity of 2e-ORR is experimentally revealed and attributed to the electronic reconfiguration on defective carbon sites induced by non-covalent dipole-dipole influence between PDA and carbon, thereby prohibiting the cleavage of O-O in OOH intermediates. This proposed strategy of dipole-dipole effects is universally applicable over 1D carbon nanotubes and 2D graphene, providing a practical route to design 2e-ORR catalysts.

Elucidating Oxygen Reduction Mechanisms on Organic Mixed Ionic-Electronic Conducting Polymers

Atmospheric oxygen is an attractive oxidant for the generation of electricity from chemical fuels and for the electrochemical production of hydrogen peroxide. Although not universal, it is generally assumed that an electrocatalyst is needed to reduce oxygen. Recently, a variety of organic mixed ionic-electronic conducting polymers (OMIECs) have been reported to exhibit catalytic behavior for both the 4-electron/4-proton and the 2-electron/2-proton oxygen reduction reaction (ORR).This work sets out to identify the oxygen reduction mechanism of OMIECs through a multi-faceted experimental and theoretical approach. We primarily focus our efforts on p(NDI-T2 P75)—a random copolymer comprised of naphthalene diimide (NDI) and bithiophene (T2) units with 75% polar sidechains—and then expand the understanding built on this system to a range of other OMIECs. Using rotating ring disk electrochemistry, we find that the investigated OMIECs exhibit a high selectivity towards the 2-electron ORR product. Using operando UV-Vis and Raman spectroscopy measurements, we identify changes in OMIEC performance when in the presence of O2. To gain further insights about the catalytic reaction path, we construct and test a microkinetic model. Through this model, we show that the performance of the tested OMIECs can be rationalized through an EC’D reaction mechanism. Our results suggest that these materials do not operate as electrocatalysts for the initial reduction of oxygen to superoxide but do function as catalysts for the disproportionation of superoxide.

Kinetic Insights into the Mechanism of Oxygen Reduction Reaction on Fe2O3 /C Composites

Electrochemical energy storage and conversion systems are the appealing replacement for nonrenewable resources to provide clean and sustainable energy. Of particular interest are fuel cells and metal-air batteries, both of which rely on the oxygen reduction reaction (ORR) for their operation. Fe-N-C catalyst has been widely used as a prominent catalyst towards ORR, but there is still some ambiguity regarding its active sites. This study describes the role of Fe2O3, an inevitable species formed in Fe-N-C catalyst towards the ORR. The Fe2O3 is carefully synthesised on various carbon supports and characterised using XPS spectra, HRTEM images, and surface area analysis. The particle size of the Fe2O3 nanoparticles synthesised on the pores of the carbon support was determined to be ~10 nm from the HRTEM analysis. The current density of ORR and the number of electrons transferred on Fe2O3/C catalysts is increased compared with bare carbon supports. Based on the kinetic analysis, the ORR on Fe2O3/C follows pseudo-4-electron (or) 2+2-electron ORR, where the first 2-electron ORR to H2O2 and second 2-electron H2O2 reduction reaction (HPRR) to H2O are assigned to the graphitic carbon (carbon defects) and Fe2O3 active sites, respectively. The role of Fe2O3 is further studied using the Theoretical method, which reveals the decreased formation of free energy of O2 adsorption. The Fe2O3 reduces the energy barrier for the reduction of *OOH to OH-. The Fe2O3/C shows higher stability by retaining 95% of the initial activity even after 20,000 cycles. Figure 1

Synthesis of Metal-Free Carbon Aerogel with Nitrogen-Doped from Pyrolysis of Cellulose Aerogels Based on Coir Fibers Using Ammonia-Urea System as Electrocatalyst of Oxygen Reduction Reaction for Cathode in Seawater Batteries

Performance of seawater batteries is still limited by the sluggish nature of oxygen reduction reaction (ORR). One way to optimize the performance of the battery is by utilizing an electrocatalyst with the ability to increase the ORR rate of reaction. Nitrogen-doped carbon aerogel based on coir fiber is one of the alternatives because of its excellent electrocatalytic performance and was made from an abundant material. Carbon aerogel was obtained from pyrolyzing coir fiber-based aerogel cellulose. Nitrogen atom structure in carbon aerogel was affected by the temperature of cellulose aerogel pyrolysis. Pyridinic N content in the Nitrogen-doped carbon aerogel has effective for the activity of the ORR. The electrocatalytic performance of the carbon aerogel synthesized from coir fiber with nitrogen doping at the pyrolysis temperature of 600 °C was investigated in this study. The research process began with the synthesis of cellulose aerogel using urea-ammonia crosslinking precursor. Next, cellulose aerogel was pyrolyzed at 600 °C to create carbon aerogel. FTIR, XRD, CV, LSV, and LP were used to characterize the samples. The carbon aerogel was N-doped with pyridinic N, according to an analysis of the FTIR spectra. The carbon aerogel shows 4-electron ORR with kinetic current density (ik) of 0.74 mA/cm2 and current density (io) of 0.583 μA/cm2, according to electrochemical performance analysis in 3.5% NaCl as electrolyte.

H2O2 electrosynthesis activity and selectivity of Pd–Te nanoparticles with different surface compositions in acidic electrolyte

The selective 2-electron oxygen reduction reaction (2e− ORR) has emerged as a promising alternative for H2O2 production to the traditional anthraquinone process, which has energy and environmental issues. H2O2 electrosynthesis in acidic electrolytes is more relevant to practical conditions but requires a much higher overpotential, where precious metal-based electrocatalysts have exhibited high efficiency for the 2e− ORR. The electrocatalytic activity and selectivity are critically affected by the surface composition of the constituent elements. However, such effects in acidic electrolytes have been rarely investigated for precious metal compounds. In this work, palladium–tellurium binary compounds with two different surface compositions were prepared, and their electrocatalytic properties were compared to reveal the structure–activity–selectivity correlations. It was found that the compound with a higher surface Te/Pd ratio exhibited higher H2O2 selectivity but lower activity due to the decreased numbers of Pd ensemble sites as well as surface Pd binding sites, respectively.

Multicomponent Synthesis of Imidazole‐Linked Fully Conjugated 3D Covalent Organic Framework for Efficient Electrochemical Hydrogen Peroxide Production

AbstractThe semiconducting properties and applications of three dimensional (3D) covalent organic frameworks (COFs) are greatly hampered because of their long‐ranged non‐conjugated skeletons and relatively unstable linkages. Here, a robust imidazole‐linked fully conjugated 3D covalent organic framework (BUCT‐COF‐7) is synthesized through the one‐pot multicomponent Debus‐Radziszewski reaction of the saddle‐shaped aldehyde‐substituted cyclooctatetrathiophene, pyrene‐4,5,9,10‐tetraone, and ammonium acetate. The semiconducting BUCT‐COF‐7, as a metal‐free catalyst, shows excellent two electron oxygen reduction reaction (ORR) activity in alkaline medium with high hydrogen peroxide (H2O2) selectivity of 83.4 %. When the BUCT‐COF‐7 as cathode catalyst is assembled into the electrolyzer, the devices showed high electrochemical production rate of H2O2 up to 326.9 mmol g−1 h−1. The accumulative amount of H2O2 could totally degrade the dye methylene blue via Fenton reaction for wastewater treatment. This is the first report about intrinsic 3D COFs for efficient electrochemical synthesis of H2O2, revealing the promising applications of fully conjugated 3D COFs in the environment‐related field.

Multicomponent Synthesis of Imidazole-Linked Fully Conjugated 3D Covalent Organic Framework for Efficient Electrochemical Hydrogen Peroxide Production.

The semiconducting properties and applications of three dimensional (3D) covalent organic frameworks (COFs) are greatly hampered because of their long-ranged non-conjugated skeletons and relatively unstable linkages. Here, a robust imidazole-linked fully conjugated 3D covalent organic framework (BUCT-COF-7) is synthesized through the one-pot multicomponent Debus-Radziszewski reaction of the saddle-shaped aldehyde-substituted cyclooctatetrathiophene, pyrene-4,5,9,10-tetraone, and ammonium acetate. The semiconducting BUCT-COF-7, as a metal-free catalyst, shows excellent two electron oxygen reduction reaction (ORR) activity in alkaline medium with high hydrogen peroxide (H2 O2 ) selectivity of 83.4 %. When the BUCT-COF-7 as cathode catalyst is assembled into the electrolyzer, the devices showed high electrochemical production rate of H2 O2 up to 326.9 mmol g-1 h-1 . The accumulative amount of H2 O2 could totally degrade the dye methylene blue via Fenton reaction for wastewater treatment. This is the first report about intrinsic 3D COFs for efficient electrochemical synthesis of H2 O2 , revealing the promising applications of fully conjugated 3D COFs in the environment-related field.

Enhanced degradation of refractory organics in ORR-EO system with a blue TiO2 nanotube array modified Ti-based Ni-Sb co-doped SnO2 anode

Recently, a novel 2-electron oxygen reduction reaction (ORR) based electro-oxidation (EO) system was developed, which utilizes a H2O2 generation cathode instead of H2 evolution cathode. A Ti-based Ni-Sb co-doped SnO2 (Ti/NATO) anode was selected for efficient degradation of refractory organics and O3 production. The synergistic reaction of O3/H2O2 further accelerated the generation of hydroxyl radicals (•OH) in the ORR-EO system. However, the catalytic activity and long-term effectiveness of the Ti/NATO anode limited the large-scale application of the ORR-EO process. In this study, a blue TiO2 nanotube array (blue-TiO2-NTA) inter-layer was introduced into the fabrication process between the Ti substrate and NATO catalyst layer. Compared to the Ti/NATO anode, the Ti/blue-TiO2-NTA/NATO anode achieved higher efficiency of organic removal and O3 generation. Additionally, the accelerated lifetime of the Ti/blue-TiO2-NTA/NATO anode was increased by 7 times compared to the Ti/NATO anode. When combined with CNTs-C/PTFE air cathode in ORR-EO system, all anodic oxidation and O3/H2O2 processes achieved higher •OH production. Over 92% of TOC in leachate bio-effluent was effectively eliminated with a relatively low energy cost of 45 kWh/t.

ZnO nanocomposites containing Cd are synthesized with high photodegradation potential for wastewater treatment

The zinc oxide (ZnO) nanoparticle on a two - electron oxygen reduction reaction is a particularly promising candidate for in-situ application. Herein, we prepared the Cd doped ZnO nanocomposites through a simple hydrothermal method. The X-ray diffraction (XRD) analysis has been carried out to confirm the structure and size of the nanomaterial. The optical absorption and energy gap of the prepared nanoparticles have been identified by UV–vis-NIR studies. Photoluminescence (PL) studies on the synthesized nanomaterials confirm the characteristic existence of blue and green emission bands. Fourier transform infrared (FTIR) spectroscopy has been studied on the ZnO nanoparticles to analyze the -OH and CO-O vibrations. The structural and surface morphology analysis was inferred by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray (EDX) microanalysis. Cd doped ZnO nanocomposites are environmentally friendly and can be utilized to quickly remove contaminants from wastewater. The findings from the adsorption equilibrium fit the Brunauer-Emmett-Teller (BET) model very well, showing multi-layer adsorption. The photodegradation studies on Cd doped ZnO nanocomposites were carried out, which is an advanced oxidation process widely used for methylene blue removal. Therefore, the higher photocatalytic performance revealed that Cd doped ZnO nanocomposites could be a promising photocatalyst for environmental remediation applications.

Efficient hydrogen peroxide production enabled by exploring layered metal telluride as two electron oxygen reduction reaction electrocatalyst

It is of great interest to develop the novel transition metal-based electrocatalysts with high selectivity and activity for two electron oxygen reduction reaction (2e− ORR). Herein, the nickel ditelluride (NiTe2) with layered structure was explored as the 2e− ORR electrocatalyst, which not only showed the highest 2e− selectivity more than 97%, but also delivered a slight activity decay after 5000 cycles in alkaline media. Moreover, when NiTe2 was assembled as the electrocatalyst in H-type electrolyzer, the on-site yield of H2O2 could reach up to 672 mmol h−1 g−1 under 0.45 V vs. RHE. Further in situ Raman spectra, theoretical calculation and post microstructural analysis synergistically unveiled that such a good 2e− ORR performance could be credited to the intrinsic layered crystal structure, the high compositional stability, as well as the electron modulation on the active site Ni atoms by neighboring Te atoms, leading to the exposure of active sites as well as the optimized adsorption free energy of Ni to –OOH. More inspiringly, such telluride electrocatalyst has also been demonstrated to exhibit high activity and selectivity towards 2e− ORR in neutral media.

Electrochemical Hydrogen Peroxide Production on Single Atoms and Atomic Clusters

The electrochemical oxygen reduction reaction (ORR) involving the transfer of two electrons (2-electron ORR) offers a sustainable alternative for the production of hydrogen peroxide (H2O2) on-site. Minimizing the use of expensive noble metal catalysts and maximizing their atomic utilization can be achieved by reducing the size of the catalysts. While previous studies have primarily focused on the relationship between particle size and oxygen reduction activity in the 4-electron ORR using Pt-based catalysts, less attention has been paid to the 2-electron ORR for H2O2 production. In this study, we prepared a series of size-controlled Pd clusters and investigated the oxygen reduction in acidic conditions to understand the relationship between cluster size and catalytic performance. Our results showed that larger Pd clusters favored the 4-electron ORR and the production of H2O, while smaller clusters favored the 2-electron ORR and the production of H2O2. To estimate the contribution of single atoms in the catalysts to their performance, we introduced CO. Using in-situ attenuated total reflection-surface enhanced infrared reflection absorption spectroscopy (ATR-SEIRAS), we observed a range of CO vibrational signatures that correlated with specific ORR behaviors depending on the particle/cluster size.

A Redox-Mediated Zinc-Air Fuel Cell

As one of the most promising power sources in converting and storing chemical energy, aqueous zinc-air batteries (ZABs) stand out because of their high theoretical energy density, low cost, high safety of aqueous electrolyte, and environmental friendliness. Three main types of ZABs including primary ZABs, mechanically rechargeable ZABs, and electrically rechargeable ZABs have been developed up to now.[1] Primary ZABs for single use are usually discarded after the Zn anode is consumed or passivated although other parts of battery remain intact, leading to enormous waste. To address it, the depleted anode and failure electrolyte can be physically replaced to recover the capacity in mechanically rechargeable ZABs. But the cumbersome disassembly/reassembly process and the performance deterioration after every recharge process limit its practical application. In addition, it is not feasible to replace zinc in some integrated systems, such as the large-scale ZAB stack. Electrically rechargeable ZABs with bifunctional oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) catalysts could be returned to the original state by electrochemical charging process, but also face some formidable challenges, such as dendritic zinc deposition, electrode deformation, and hydrogen evolution, limiting the long-term cycling performance. Besides, sluggish kinetics of ORR/OER and Zn passivation result in low energy efficiency, limited depth of discharge and power density. Especially in the resource-constrained and off-grid region, there isn’t external electricity source to charge the electrically rechargeable ZABs which limits their applications. Moreover, the reactions inherently take place on the surface of Zn anode and air cathode, in which the storage and conversion capability of the cell would be essentially constrained by the surface area of electrode and the volume of electrode compartment.The concept of redox targeting (RT) of battery materials offers a feasible solution to address these issues by employing redox mediators (RMs). To tackle the above challenges, here we demonstrate a redox-mediated Zn-air fuel cell (RM-ZAFC) based on the RT reactions of cobalt triisopropanolamine complex (CoTiPA) with O2 and 7,8-dihydroxy-2-phenazinesulfonic acid (DHPS) with Zn metal in the catholyte and anolyte, respectively. Both the 4-electron (4 e-) ORR and Zn oxidation reactions are liberated from the electrode surface and occur inside separate reactor tanks resorting to the RT processes. Upon operation, Co(III)TiPA in the catholyte is electrochemically reduced to Co(II)TiPA on the cathode and chemically oxidized back through ORR in the gas diffusion tank (GDT) into which O2 is fed. In conventional ZABs, ORR takes place on the triple-phase reaction interface of the heterogeneous electrocatalyst, and the catalytic performance is closely related to the density of exposed active site, electrical conductivity and reaction energy barrier. As compared, the redox-mediated ORR in GDT occurs homogeneously in the catholyte in which the dissolved RM could provide a large quantity of rection sites with tunable reaction energy barrier. For the negative side, DHPS-2H is firstly oxidized to DHPS on the anode and circulated into anodic tank, where it is regenerated by oxidizing Zn to ZnO. The discharge product ZnO is formed and deposited on the Zn granules loaded in the tank. After fully discharged, the cell can be feasibly refueled by replacing the Zn granules in the tank instead of disassembling and reassembling the whole cell. In this RM-ZAFC, the energy storage unit is decoupled from the power generation unit, thus offering greater operation flexibility and system scalability with modular design than the conventional ZABs. Compared with the commercial hydrogen tank used in hydrogen fuel cells, Zn granules loaded in the anodic tank present much higher volumetric capacity, greater safety and ease for storage and transportation. Therefore, as an energy conversion and storage device, RM-ZAFC would have great promise for automotive, backup, and stationary power applications.[2] In addition, we also propose an efficient and zinc regeneration method by RT reaction between RM and the product ZnO in RM-ZAFC to avoid the waste of ZnO and reduce the cost.

Efficient electrocatalytic two-electron oxygen reduction over aminophenol formaldehyde resin-derived carbon microspheres

The electrocatalytic 2-electron oxygen reduction reaction (2e-ORR) to hydrogen peroxide (H2O2) required cheap and efficient electrocatalytic materials. Herein cheap 3-aminophenol formaldehyde resin microspheres were synthesized at a large scale of about 15 g in one run. By annealing it, nitrogen-doped carbon spheres could be conveniently obtained, which was found to be efficient electrocatalyst for 2e-ORR with the highest H2O2 selectivity of about 94% at 0.4 V vs RHE. The electrolysis H2O2 production rate over N-doped carbon in 0.1 M KOH solution reached 48 mmol gcat-1h−1. Aminophenol formaldehyde resin-derived carbon provided a cheap and effective catalyst for electrocatalytic H2O2 production.

Activating the PdN4 single-atom sites for 4 electron oxygen reduction reaction via axial oxygen ligand modification

The absence of Pd ensemble sites and weak affinity for O-intermediates in tetracoordinate planar PdN4 sites inhibit O-O bond dissociation and restrict 4e- oxygen reduction reaction (ORR) pathway. Optimizing the adsorption energy between O-intermediates and PdN4 sites is a rational approach for selectively promoting 4e- ORR electrocatalysis. Herein, we propose a molten-salt strategy for introducing axial oxygen ligand into the PdN4 sites to manipulate the electronic structure and create catalytic O-PdN4 sites (one subsurface axial Pd-O configuration on PdN4 plane) on N-doped graphene nanosheets (O-PdN4-NGS). Density functional theory calculations revealed that the axial Pd-O coordination can induce charge redistribution, downshift the d-band center of Pd and enhance the adsorption affinity of PdN4 site for O-intermediates, thereby leading to superior electrocatalysis activity and selectivity for 4e- ORR process compared to conventional PdN4 sites in 0.1 M KOH (with a positive half-wave potential E1/2 of 0.90 V vs RHE). Moreover, zinc-air battery featuring with O-PdN4 sites delivers a peak power density of 178 mW cm−2 at 227.5 mA cm−2 and stable long-term cycling performance, effectively showcasing the advantages of the axial O ligand modification in practical application. This work provides a constructive strategy to activate the reaction activity and specificity of PdN4 single-atom sites by precisely-tuning the local coordination environment of Pd.