Oxygen Reduction Reaction Performance Research Articles

Core/shell Ni@C particle-supported N-doped carbon with hollow capsules for efficient electrocatalytic reduction of oxygen

To replace the noble metal catalysts for oxygen reduction reaction (ORR), a Ni@C-supported N-doped carbon material (Ni@C/NC) is in-situ prepared via one-step pyrolyzing the polymerizable ionic liquid of vinyl imidazole combined with Ni(NO3)2. Systemic investigations demonstrate that these nanosized Ni particles are tightly wrapped with a thin carbon layer to form the core/shell structure, meanwhile carbon capsules are synchronously yielded on the carbon matrix. As a result, both the carbon shell and the carbon capsule jointly increase the active sites of the Ni@C/NC, while the carbon shell also contributes the fast electron-transfer from Ni particle. Compared with the normal Ni-supported carbon catalyst, the Ni@C/NC shows the respectable ORR performance with the onset and half-wave potentials of 0.96 and 0.84 VRHE. After the long-term electrocatalysis (10 h), the Ni@C/NC is found to possess the great structural and electrocatalytic stabilities, which maintains 93 % of the initial current density and the well-dispersed and uniform Ni@C particles. Subsequently, a Zn-Air battery with the Ni@C/NC cathode is assembled and exhibits a peak power density of 200 mW cm−2. Therefore, the as-obtained Ni@C/NC with the high electroactivity and stability can be expected as an ideal candidate to apply in the metal-air batteries and fuel cells in the future.

Suppressing the hydrogen bonding interaction with *OOH toward efficient H2O2 electrosynthesis via remote electronic tuning of Co-N4

The non-covalent interaction that appears along with electronic tuning is often overlooked in interpreting the oxygen reduction reaction (ORR) dynamics, resulting in a limited understanding of the governing principles. Herein, through intricately engineering pedant substituents on porphyrins backbones, Co-N4 moieties featuring varied electronic configurations served as an exemplary model to elucidate the role of hydrogen bonding interaction appears along with electronic tuning in determining 2e- ORR performance. Co-TEPP with an electron-deficient Co-N4 moiety emerges as a standout performer for O2-to-H2O2 conversion. Upon covalently linking the Co-TEPP monomer on rGO to form robust organic polymer structures (Co-TEPP-COP/rGO), superior H2O2 selectivity (> 95 %), remarkable H2O2 production rate (∼18.8 mol gcat−1 h−1), and excellent performance durability are identified. Such optimized H2O2 electrosynthesis could be attributed to the suppressed hydrogen bonding interaction between *OOH and electron-deficient Co-N4 moiety, which consequently weakens *OOH binding strength to favor H2O2 electrosynthesis.

Pyridinic-N Regulated Electron Injection to Modulate *OH Adsorption at Fe-N-C Sites for an Efficient Oxygen Reduction Reaction.

To enhance the efficiency of oxygen reduction reaction (ORR) catalysts, precise control over the adsorption/desorption energy barriers of oxygen intermediates at atomically dispersed Fe-N-C sites is essential yet challenging. Addressing this, we employed a pyrolysis approach using a nitrogen-containing polymer to fabricate Fe single-atom (SA) catalysts embedded in a pyridinic-N enriched carbon matrix. This synthesis strategy yielded Fe SAs that demonstrated a superior electrochemical ORR performance, evidenced by an impressive half-wave potential of 0.941 V and a high limiting current density of 5.72 mA/cm2. Moreover, when applied in homemade Zn-air batteries, this premier catalyst exhibited exceptional specific capacity (720 mAh/gZn), peak power density (253 mW/cm2), and notable long-term stability. Theoretical insights revealed that the increased pyridinic-N content in the catalyst facilitated efficient electron transfer from N atoms to the Fe active sites, thus fine-tuning the d-band center and effectively controlling the adsorption energy barrier of *OH species. These mechanisms synergistically improve the ORR performance. Crucially, this fabrication method shows promise for adaptation to other transition metal-based SAs, including Co, Ni, and Cu, potentially establishing a versatile synthesis route for developing atomically dispersed catalyst systems in future applications.

Nitrogen and sulfur incorporated chitosan-derived carbon sphere hybrid MXene as highly efficient electrocatalyst for oxygen reduction reaction

The quest for non-precious electrocatalysts through biomass for energy applications has attracted keen interest, but optimization for fuel cells remains challenging. Herein, we have developed a nitrogen and sulfur-anchored MXene hybrid chitosan-derived carbon sphere (N,S-MXC) reporting for the first time as a novel oxygen reduction reaction (ORR) electrocatalyst. Interestingly, as the mass ratio of MXene to Chitosan varied by (1:2, 1:1, and 2:1), the microstructures of the as-prepared catalysts changed, which drastically influenced the corresponding ORR performance. Notably, when the mass ratio was maintained to be 1:2, Ti3C2 nanoparticles were dispersed on the surface of the biomass carbon core shell. They created multimodal porous morphology that helps to facilitate faster electron transfer, resulting in a high onset-potential of 0.89 V and limiting current density of −4.2 mA/cm2 as well as excellent durability with minimum half-wave potential loss of 2.3 mV after 5000 cyclic voltammetry (CV) cycles than benchmark Pt/C. In addition, the corresponding catalyst also possessed robust stability of 87.47 % and an excellent methanal poisoning tolerance effect in an alkaline medium. In a nutshell, this work paves the pathway for converting sea animal waste to develop porous carbon as supporting material for fuel cells that directly or indirectly support achieving carbon neutrality.

Anisotropic Heterobimetallic Nanomaterials with Controlled Composition for Efficient Oxygen Reduction at Ultralow Loading

AbstractHydrogen fuel cells represent a leading technology in developing green energy targeting net‐zero emissions goals by mid‐century. However, the sluggish kinetics of the oxygen reduction reaction (ORR) have hitherto demanded substantial quantities of expensive platinum (Pt) group metals. Advances in catalyst design, including the controllable fabrication of highly branched morphologies to increase the surface area‐to‐volume ratio, intermixing Pt with more affordable transition metals, and controlling composition, offer solutions that can further enhance activity and reduce expense. In this context, Pt/M (M = Fe, Ni, Co) nanopods and nanodendrites with precise composition control using more affordable starting materials are designed and crafted. The method is highly efficient, taking only 30 min and avoiding the need for high‐pressure equipment, making it highly scalable. These catalysts show superior ORR performance at an electrode loading as low as 0.0022 mgPt cm−2. One, nanodendritic Pt/Ni, achieves a mass activity of at 0.9 V versus RHE, making it 87 times more efficient in terms of Pt‐content than a commercial 10 wt% Pt/C nanoparticle standard. These findings provide new opportunities for developing next‐generation, cost‐efficient Pt‐based catalysts, by potentially advancing hydrogen fuel cell technology through performance enhancement and addressing cost challenges through catalyst design.

Engineering Synergetic Fe‐Co Atomic Pairs Anchored on Porous Carbon for Enhanced Oxygen Reduction Reaction

AbstractThe rational design of heteronuclear dual‐atom catalyst (DAC) is intricate due to the random dispersion of metal atoms under thermal treatment. Herein, a novel precursor pre‐orientation strategy is reported to construct Fe‐Co diatomic sites atomically dispersed on nitrogen doped carbon (Fe‐Co‐NC) via cubic Prussian blue analogue as metal source. Due to the specific synergy between Fe and Co centers, the obtained Fe‐Co‐NC catalyst renders outstanding oxygen reduction reaction (ORR) performance with positive half‐wave potential and good durability in wide pH range. Density functional theory further clarifies the active centers and reveals that the Fe‐Co‐NC dual atomic catalyst follows the modulation mechanism, where the intermediates tended to adsorb on Fe site, while the neighboring Co atom can assist by lowering the d‐band center of Fe site. Experimentally and theoretically emphasizes the priority of heteronuclear diatomic Fe‐Co catalysts over homonuclear Fe‐Fe‐NC and Co‐Co‐NC DAC. Moreover, the Zn‐Air battery (ZAB) and microbial fuel cell (MFC) assembled with Fe‐Co‐NC cathodes both exhibit splendid power density (382 mW cm−2 for ZAB, 2034 ± 103 mW m−2 for MFC) as well as excellent stability. This work provides a new perspective for rational construction and precise regulation for heteronuclear dual‐atom catalysts.

High performance oxygen reduction and evolution reactions by graphitization of nickel –cobalt framework system

This study presents the successful synthesis of metal-organic frameworks (MOFs) via a simple one-pot method, followed by pyrolysis at 1000 °C to be used in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A study utilizing various techniques, including field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and X-ray diffraction (XRD), investigated the properties of NiCo-MOF and its individual components before and after pyrolysis.The pristine MOFs exhibited limited electrochemical stability for both ORR and OER, while the pyrolyzed MOFs demonstrated a significant enhancement and excellent long-term stability in OER and ORR performance in alkaline media. Notably, the OER performance rivaled that of the benchmark IrO2 electrocatalyst, with similar onset potentials (1.48 V for IrO2, 1.52 V, 1.56 V, and 1.59 V for pyrolyzed NiCo-MOF, Co-MOF, and Ni-MOF, respectively). Furthermore, the pyrolyzed MOF catalysts displayed promising ORR activity in a 0.1 M KOH solution under O2 saturation, as evidenced by their onset potentials (around 0.615 V, 0.63 V, and 0.7 V vs. RHE) and favorable Tafel slopes (53, 84, and 154 mV dec⁻1, for graphitizated Ni-MOF, Co-MOF, and NiCo-MOF, respectively). These findings demonstrate the effectiveness of pyrolysis in engineering the MOF crystal structure for enhanced catalytic performance. This paves the way for further exploration of this synthesis method for the design of structurally optimized catalysts and applicable to a broad spectrum of energy technologies.

P-d Orbital Hybridization Induced by Asymmetrical FeSn Dual Atom Sites Promotes the Oxygen Reduction Reaction.

With more flexible active sites and intermetal interaction, dual-atom catalysts (DACs) have emerged as a new frontier in various electrocatalytic reactions. Constructing a typical p-d orbital hybridization between p-block and d-block metal atoms may bring new avenues for manipulating the electronic properties and thus boosting the electrocatalytic activities. Herein, we report a distinctive heteronuclear dual-metal atom catalyst with asymmetrical FeSn dual atom sites embedded on a two-dimensional C2N nanosheet (FeSn-C2N), which displays excellent oxygen reduction reaction (ORR) performance with a half-wave potential of 0.914 V in an alkaline electrolyte. Theoretical calculations further unveil the powerful p-d orbital hybridization between p-block stannum and d-block ferrum in FeSn dual atom sites, which triggers electron delocalization and lowers the energy barrier of *OH protonation, consequently enhancing the ORR activity. In addition, the FeSn-C2N-based Zn-air battery provides a high maximum power density (265.5 mW cm-2) and a high specific capacity (754.6 mA h g-1). Consequently, this work validates the immense potential of p-d orbital hybridization along dual-metal atom catalysts and provides new perception into the logical design of heteronuclear DACs.

Designing highly efficient electrocatalyst for ORR and OER of transition metals doped g-C9N7: A density functional theory study

The application of fuel cells and metal-air batteries is limited by the rate of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Thus, the aim of this study is to find an efficient electrocatalyst to accelerate the reaction rate by DFT method. The structures of VIIB, VIII, IB, and IIB groups transition metals doped g-C9N7 as superb bifunctional electrocatalysts for ORR and OER are probed. The results show that Fe-, Pd-, and Au–C9N7 possess the superb ORR performance with the ORR overpotentials values of 0.35, 0.40, and 0.39 V, which gives them better performance than Pt(111). Moreover, Rh-, Pd-, and Pt–C9N7 have better OER performance with the OER overpotentials values of 0.30, 0.57, and 0.43 V, which makes them comparable to RuO2(110) and IrO2(110). Finally, the calculated bifunctional index (BI) results show that Pd–C9N7 can be used as an excellent bifunctional electrocatalyst because it has a minimum BI value of 0.97 V. This research has the potential to provide valuable theoretical direction into the use of M − C9N7 as electrocatalysts for both the ORR and OER.

Long‐Durability, Surfactant‐Free, and Bifunctional Ir‐Doped Pt3Co/MWCNTs Electrocatalysts towards ORR and OER in Acidic Media

AbstractDeveloping cost‐effective, high‐performance, and durable electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is pivotal for advancing hydrogen energy conversion and storage technologies. Simultaneously, establishing scalable methods for their production is essential for the widespread adoption of these renewable energy solutions. In this study, we present a successful large‐scale synthesis of surfactant‐free iridium‐doped Pt−cobalt nanoparticles supported on multiwalled carbon nanotubes (Ir−Pt3Co/MWCNTs). This composite demonstrates significantly enhanced ORR and OER activity compared to commercial Pt/C and IrO2 in acidic environments. The Ir−Pt3Co/MWCNTs catalyst composite exhibits a low overpotential of 357 mV at 10 mA cm−2 and a remarkable mass activity of 0.594 A/mgPt. Investigating the influence of Ir doping content on ORR and OER, we found that Pt3Co0.6Ir0.4/MWCNTs showcased the most superior activity in both reactions. We present a reproducible protocol for the synthesis of surfactant‐free Ir−Pt3Co nanoparticles supported on MWCNTs, yielding a bifunctional catalyst capable of efficiently catalyzing both ORR and OER with outstanding efficiency and stability in acidic media. Detailed X‐ray photoelectron spectroscopy (XPS) analysis elucidates the electron transfer between atoms, optimizing the electronic structure and adjusting the position of the d‐band. This optimization enhances the electrocatalytic activity and structural stability of the catalysts, contributing to their superior performance in ORR and OER.

Fe based MOF encapsulating triethylenediamine cobalt complex to prepare a FeN3-CoN3 dual-atom catalyst for efficient ORR in Zn-air batteries

Single-atom catalysts show good oxygen reduction reaction (ORR) performance in metal-air battery. However, the symmetric electron distribution results in discontented adsorption energy of ORR intermediates and a lower ORR activity. Herein, Fe-Co dual-atom catalyst with FeN3-CoN3 configuration was prepared by encapsulating nitrogen-rich ion (triethylenediamine cobalt complex, [Co(en)3]3+) in Fe based MOF cage to greatly enhance ORR performance. Due to the confinement effect of the MOF cage, the encapsulated [Co(en)3]3+ is closer to Fe of MOF, thus easily generating FeN3-CoN3 sites. The FeN3-CoN3 sites can break the symmetric electron distribution of single-atom sites, optimizing adsorption energy of oxygen intermediate. Thus, FeCo-NC exhibits extraordinary ORR activity with a high half-wave potential of 0.915 V and 0.789 V in alkaline and acidic electrolyte, respectively, while it was 0.874 V and 0.79 V for Pt/C. The liquid and solid Zn-air batteries with FeCo-NC as cathode show higher peak power density and specific capacity. DFT results indicate that FeN3-CoN3 site can reduce the reaction energy barrier of the rate-determining step resulting in an excellent ORR performance.

Electron Donor–Acceptor Activated Single Atomic Sites for Boosting Oxygen Reduction Reaction

AbstractFabricating efficient non‐platinum‐group‐metal catalysts for the oxygen reduction reaction (ORR) in proton‐exchange membrane fuel cells still remains a big challenge. This study creates a unique bamboo‐like architecture of Mn and Fe single atomic sites (SASs) anchored on core‐shell structure of nanopaticles@carbon nanotubes (MnFe SASs/NPs@CNTs) via a precursor route, where the Fe nanoparticles (NPs) (identified as γ‐Fe and Austenite) are confined into CNTs, such an architecture exhibits compelling ORR activity and durability in 0.1 m HClO4. Experiments and calculations both reveal that the electron donor–acceptor paradigm between Mn SASs and Fe NPs launches a lattice‐electron coupling mechanism not only increasing occupation of π‐antibonding orbital in Mn−*O intermediates but also rising Jahn–Teller effect, thereby destabilize the Mn−*O intermediate and eventually facilitate the potential‐limiting step from *O to *OH. Such a coupling activation of the ORR‐inert Mn SASs greatly improves ORR performances of MnFe SASs/NPs@CNTs.

In-situ construction of ionic liquid salt-derived graphene-like dual-heteroatoms doping engineering as efficient metal-free electrocatalyst for oxygen reduction reaction

Metal-free heteroatom-doped carbon catalysts can effectively eliminate the degradation and pollution problems caused by metal dissolution. However, single heteroatom doping often restricts the regulation of geometric and electronic structures for oxygen reduction reaction (ORR) electrocatalysts. Herein, a dual atomic doping engineering to optimize the electronic structure and local coordination environment of ionic liquid salt-derived graphene-like host material as an efficient metal-free electrocatalyst for ORR. The resultant PNG catalyst with a typical nanosheets morphology with a high specific surface area and unique hierarchical porous structure. Benefiting from the uniform doping of P, N heteroatoms, graphene-like structure, optimized electronic structure and coordination environment, thus-prepared PNG-2 exhibits outstanding ORR activity, which the onset potential and half-potential are negatively shifted by around 70 mV and 46 mV, respectively, as compared to the commercial Pt/C (20 wt.%) for ORR. Furthermore, the PNG-2 exhibits the higher diffusion limiting current density, superior long-term stability as well as excellent resistance to methanol oxidation than Pt/C. Experimental studies and density functional theory (DFT) calculations reveal that the enhanced chemisorption of oxygen species (*OOH, *O and *OH) onto the P and N sites of the PNG catalysts can effectively accelerate the charge transfer kinetics and promote a favorable ORR performance.

Prussian Blue Analogues Derived Bimetallic CoNi@NC as Efficient Oxygen Reduction Reaction Catalyst for Mg‐Air Batteries

The magnesium‐air (Mg‐air) batteries are regarded as a highly promising system for electrochemical energy conversion and storage, owing to exceptional energy density, notable safety and eco‐friendliness. The development of high‐performance and durable non‐noble metal catalysts for the cathodic oxygen reduction reaction (ORR) is crucial for advancing the practical use of Mg‐air batteries. The synergistic interaction between different metals in bimetallic catalysts is an effective strategy for enhancing the activity and stability of the catalysts. Herein, various prussian blue analogues (PBA) were selected as precursors to synthesis the bimetallic CoNi@NC, monometallic Co@NC and Ni@NC catalysts due to tunable chemical compositions. Compared with Co@NC and Ni@NC, the bimetallic CoNi@NC pyrolyzed at 600°C (CoNi@NC‐600) exhibits outstanding ORR performances and stability in alkaline (0.1 M KOH) and neutral (3.5 wt% NaCl) electrolytes. Following 5000 CV cycles, the half‐wave potentials for CoNi@NC‐600 show only minor negative shifts of 8 and 7 mV, respectively. Meanwhile, the CoNi@NC‐600 possesses the similar ORR reaction mechanism and activity with Pt/C. The primary Mg‐air battery assembled with CoNi@NC‐600 displays better discharge performances than that of Co@NC and Ni@NC. This study lays the foundation for future investigations into the advancement of non‐precious bimetallic catalysts for ORR in Mg‐air batteries.

Highly dispersed Co nanoparticles confined by mesopore-rich N-doped hollow carbon nanotubes for efficient oxygen reduction reaction and Zn-air battery

Oxygen reduction reaction (ORR) is an important reaction process in Zn-air batteries, and the catalyst plays a crucial role as the cathode in the system. However, the reported catalysts often exhibit poor durability and stability in the operation of air batteries. Here, we used g-C3N4 as a precursor to mix Co nanoparticles for carbonization, and synthesized a large number of carbon nanotubes (CNTs) interwoven cluster catalysts, namely Co/CNT-800. The obtained catalyst has a rolling grass like morphology, forming a highly conductive network, which helps to improve the electron transfer ability in the ORR process. At the same time, the influence of materials at different carbonization temperatures on the ORR of Zn-air batteries was studied. In alkaline media, Co/CNT-800 showed the high ORR performance, with a half-wave potential of 0.839 V (vs. RHE, Pt/C 0.845 V). After 5000 cycles, the E1/2 of the Co/CNT-800 catalyst only decreased by 9 mV, and its performance in stability tests and methanol tolerance tests was superior to Pt/C. When Co/CNT-800 catalyst is used as the air cathode for Zn-air batteries, it exhibits an excellent specific capacity of 709.2 mAh/g and a power density of 142.2 mW cm−2.This research achievement provides valuable insights for the development of high-performance Zn-air batteries and innovative guidance for the design of ORR catalysts.

Boosting electrochemical oxygen reduction to hydrogen peroxide coupled with organic oxidation

The electrochemical oxygen reduction reaction (ORR) to produce hydrogen peroxide (H2O2) is appealing due to its sustainability. However, its efficiency is compromised by the competing 4e− ORR pathway. In this work, we report a hierarchical carbon nanosheet array electrode with a single-atom Ni catalyst synthesized using organic molecule-intercalated layered double hydroxides as precursors. The electrode exhibits excellent 2e− ORR performance under alkaline conditions and achieves H2O2 yield rates of 0.73 mol gcat−1 h−1 in the H-cell and 5.48 mol gcat−1 h−1 in the flow cell, outperforming most reported catalysts. The experimental results show that the Ni atoms selectively adsorb O2, while carbon nanosheets generate reactive hydrogen species, synergistically enhancing H2O2 production. Furthermore, a coupling reaction system integrating the 2e− ORR with ethylene glycol oxidation significantly enhances H2O2 yield rate to 7.30 mol gcat−1 h−1 while producing valuable glycolic acid. Moreover, we convert alkaline electrolyte containing H2O2 directly into the downstream product sodium perborate to reduce the separation cost further. Techno-economic analysis validates the economic viability of this system.

One single-atom Mn doping strategy enabling two functions of oxygen reduction reaction and pseudocapacitive performance

Single-atom metal species as highly effective active sites are crucial for enhancing energy storage and conversion properties. However, achieving the simultaneous construction of single-atom sites and the regulation of matrix structures to enable their application in both energy storage and conversion remains a challenge. Here, we have successfully developed unique MnN2C2 active sites, atomically dispersed on N-doped mesoporous graphitic carbon sheets (MnSAs/NMC). This is accomplished through the strategic utilization of MnCl2 salt, which serves dual roles of a pore-forming agent and a template. The MnSAs/NMC catalyst demonstrates compelling electrocatalytic activity for the oxygen reduction reaction (ORR), with an impressive half-wave potential (E1/2 = 0.90 V), alongside superior capacitance reaching 444 F g-1 at 0.5 A g-1 for supercapacitors. Crucially, both experimental and theoretical simulations validate that the single-atom dispersed MnN2C2 optimizes the adsorption energy of reactants and intermediates in the ORR process and pseudocapacitive behavior, leading to excellent ORR activity and capacitive performance. Interestingly, MnSAs/NMC-based Zn-air batteries exhibit concurrently high-power density derived from capacitive property and high energy density enhanced by ORR process. This study presents a novel preparation method for single-atom catalysts, which paves the way for the commercial application of super energy storage and conversion devices.

Creating Asymmetric Fe-N3C-N Sites in Single-Atom Catalysts Boosts Catalytic Performance for Oxygen Reduction Reaction.

Fine tuning of the metal site coordination environment of a single-atom catalyst (SAC) to boost its catalytic activity for oxygen reduction reaction (ORR) is of significance but challenging. Herein, we report a new SAC bearing Fe-N3C-N sites with asymmetric in-plane coordinated Fe-N3C and axial coordinated N atom for ORR, which was obtained by pyrolysis of an iron isoporphyrin on polyvinylimidazole (PVI) coated carbon black. The C@PVI-(NCTPP)Fe-800 catalyst exhibited significantly improved ORR activity (E1/2 = 0.89 V vs RHE) than the counterpart SAC with Fe-N4-N sites in 0.1 M KOH. Significantly, the Zn-air batteries equipped with the C@PVI-(NCTPP)Fe-800 catalyst demonstrated an open-circuit voltage (OCV) of 1.45 V and a peak power density (Pmax) of 130 mW/cm2, outperforming the commercial Pt/C catalyst (OCV = 1.42 V; Pmax = 119 mW/cm2). The density functional theory (DFT) calculations revealed that the d-band center of the asymmetric Fe-N3C-N structure shifted upward, which enhances its electron-donating ability, favors O2 adsorption, and supports O-O bond activation, thus leading to significantly promoted catalytic activity. This research presents an intriguing strategy for the designing of the active site architecture in metal SACs with a structure-function controlled approach, significantly enhancing their catalytic efficiency for the ORR and offering promising prospects in energy-conversion technologies.

Asymmetric cobalt porphyrins for pH-universal oxygen reduction reactions: Benzoic acid advances phenyl as substituents

Asymmetric metalloporphyrins are potential electrocatalysts to construct composites for efficient oxygen reduction reactions (ORRs) due to their inherent large dipole moment, which facilitates the charge separation. To find more effective molecular structures towards the ORRs, in particular their performance and electrolyte relationship, we rationally designed two A3B-type asymmetric cobalt porphyrin aPh-TCoP and aBA-TCoP with phenyl and benzoic acid as substituents, respectively. The ORR performance of the porphyrin-decorated carbon black composites was examined in five electrolytes at different pH values spanning from 0.7 to 13.7. It was found that aBA-TCoP/C exhibited better ORR activity and selectivity than aPh-TCoP/C in all solutions. Interestingly, both composites demonstrated their highest ORR activity in the pH13.7 electrolyte and exhibited 4-electron selectivity in the pH3.7 solution. This conclusion is drawn from a comprehensive analysis of various electrochemical properties, encompassing current density, reduction potentials, electron transfer numbers, and intermediate yields. The results illustrate the regulation of ORR properties by altering the electrolyte pH and a notable improvement in the ORR performance through the modification of porphyrin substituents. These findings offer a foundational understanding for the design of efficient metalloporphyrins and the attainment of controlled oxygen reduction in electrochemical devices.

Spatially confined radical addition reaction in the sub-nanometer scaled interlayers of electrochemically expanded graphene sheets

Here we report a spatially confined radical addition reaction which occurs in the sub-nanometer scaled interlayers of the expanded graphene sheets during the electrochemical exfoliation processes of graphite. Due to its chemical stability, challenge remains to functionalize graphene simultaneously during the preparation processes. To this, we use tetrachloroaluminate (AlCl4−) as the co-intercalation anions together with sulfate (SO42−) for the electrochemical exfoliation of graphite. We revealed the extremely irreversible intercalation of AlCl4− ions in graphite layers and the generation of C–Cl bonds during electrolysis. Chlorine and oxygen were homogeneously distributed on the basal plane of the obtained graphene, and the controlled functionalization was achieved by tuning the concentration of AlCl4− anions in the electrolyte solution, indicating the spatially confined chlorine addition reaction occurring between the sub-nanometer interlayers of expanded graphite. Furthermore, the chlorine and oxygen hybrid-substituted graphene exhibited excellent electrocatalytic performance for oxygen reduction reaction. This work demonstrates an innovative radical addition reaction in the confined space at nanometer or subnanometer scale and, meanwhile, provides a direct functionalization of graphene during the electrochemical exfoliation of graphite.