Two-electron Oxygen Reduction Reaction Research Articles

Heavily Doped Carbon Nitride Nanocrystal Promotes Visible-Near-Infrared Photosynthesis of Hydrogen Peroxide with Near-Unit Photon Utilization.

Direct photosynthesis of hydrogen peroxide (H2O2) from water and oxygen represents an intriguing alternative to the current indirect process involving the reduction and oxidation of quinones. However, limited light utilization and sluggish charge transfer largely impede overall photocatalytic efficiency. Herein, we present a heavily doped carbon nitride (CNKLi) nanocrystal for efficient and selective photoproduction of H2O2 via a two-electron oxygen reduction reaction (ORR) pathway. CNKLi induces metal-to-ligand charge transfer (MLCT) and electron trapping, which broadens the light absorption to the visible-near-infrared (vis-NIR) spectrum and prolongs the photoelectron lifetime to the microsecond time scale with an exceptional charge diffusion length of ∼1200 nm. Near-unit photoutilization with an apparent quantum yield (AQY) of 100% for H2O2 generation is achieved below 420 nm. Impressively, CNKLi exhibits an appreciable AQY of 16% at 700 nm, which reaches the absorption capacity (∼16%), thus suggesting a near-unit photon utilization <700 nm. In situ characterization and theoretical calculations reveal the facilitated charge transfer from K+ to the heptazine ring skeleton. These findings provide an approach to improve the photosynthetic efficiency of direct H2O2 preparation in the vis-NIR region and expand applications for driving kinetically slow and technologically desirable oxidations or high-value chemical generation.

Isomerization Engineering of Oxygen-Enriched Carbon Quantum Dots for Efficient Electrochemical Hydrogen Peroxide Production.

Hydrogen peroxide (H2O2) has emerged as a kind of multi-functional green oxidants with extensive industrial utility. Oxidized carbon materials exhibit promises as electrocatalysts in the two-electron (2e-) oxygen reduction reaction (ORR) for H2O2 production. However, the precise identification and fabrication of active sites that selectively yield H2O2 present a serious challenge. Herein, a structural engineering strategy is employed to synthesize oxygen-doped carbon quantum dots (o-CQD) for the 2e- ORR. The surface electronic structure of the o-CQDs is systematically modulated by varying isomerization precursors, thereby demonstrating excellent electrocatalyst performance. Notably, o-CQD-3 emerges as the most promising candidate, showcasing a remarkable H2O2 selectivity of 96.2% (n = 2.07) at 0.68V versus RHE, coupled with a low Tafel diagram of 66.95mV dec-1. In the flow cell configuration, o-CQD-3 achieves a H2O2 productivity of 338.7mmol gcatalyst -1 h-1, maintaining consistent production stability over an impressive 120-hour duration. Utilizing in situ technology and density functional theory calculations, it is unveil that edge sites of o-CQD-3 are facilely functionalized by C-O-C groups under alkaline ORR conditions. This isomerization engineering approach advances the forefront of sustainable catalysis and provides a profound insight into the carbon-based catalyst design for environmental-friendly chemical synthesis processes.

Bimetallic Center Metal–Organic Framework Catalysts for the Two-Electron Oxygen Reduction Reaction

Bimetallic Center Metal–Organic Framework Catalysts for the Two-Electron Oxygen Reduction Reaction

Electronic Metal-Support Interactions Boost *OOH Intermediate Generation in Cu/In2Se3 for Electrochemical H2O2 Production.

Two-electron oxygen reduction reaction (2e- ORR) is a promising method for the synthesis of hydrogen peroxide (H2O2). However, high energy barriers for the generation of key *OOH intermediates hinder the process of 2e- ORR. Herein, we prepared a copper-supported indium selenide catalyst (Cu/In2Se3) to enhance the selectivity and yield of 2e- ORR by employing an electronic metal-support interactions (EMSIs) strategy. EMSIs-induced charge rearrangement between metallic Cu and In2Se3 is conducive to *OOH intermediate generation, promoting H2O2 production. Theoretical investigations reveal that the inclusion of Cu significantly lowers the energy barrier of the 2e- ORR intermediate and impedes the 4e- ORR pathway, thus favoring the formation of H2O2. The concentration of H2O2 produced by Cu/In2Se3 is ~2 times than In2Se3, and Cu/In2Se3 shows promising applications in antibiotic degradation. This research presents a valuable approach for the future utilization of EMSIs in 2e- ORR.

Heterostructure and interface engineering of Ni0.85Se-MoSe2@PEI for enhancing electrocatalytic acidic oxygen reduction to hydrogen peroxide

Two-electron oxygen reduction reaction (2e− ORR) for hydrogen peroxide (H2O2) production in acidic solution is becoming a promising synthetic method due to its mild and green process. However, it is still hindered by sluggish kinetics and low selectivity. Given that heterostructure can enhance electron transfer and provide abundant active sites, interface modification can optimize O2 adsorption configurations and the adsorption energy of the reaction intermediates to improve ORR activity and selectivity. Here, we coupled heterostructures of Ni0.85Se-MoSe2 and polyethyleneimine (PEI) functionalization to enhance the activity and selectivity of the 2e− ORR for the efficient production of H2O2 in acidic solutions. The as-fabricated Ni0.85Se-MoSe2@PEI performed 91.7 % selectivity of H2O2 in the rotating ring-disk electrode test, while the H2O2 yield rate was up to 3.57 mol gcat.−1h−1 and the Faraday efficiency was 95.5 % in the H-type cell. In addition, Ni0.85Se-MoSe2@PEI maintains excellent stability in long-term operation, verifying the practicability of the catalyst. The combination of heterostructure and interface engineering provides research ideas for the electrochemical synthesis of H2O2.

Validating ΔΔG Selectivity Descriptor for Electrosynthesis of H2O2 from Oxygen Reduction Reaction.

Understanding selectivity trends is a crucial hurdle in the developing innovative catalysts for generating hydrogen peroxide through the two-electron oxygen reduction reaction (2e-ORR). The identification of selectivity patterns has been made more accessible through the introduction of a newly developed selectivity descriptor derived from thermodynamics, denoted as ΔΔG introduced in Chem Catal. 2023, 3(3), 100568. To validate the suitability of this parameter as a descriptor for 2e-ORR selectivity, we utilize an extensive library of 155 binary alloys. We validate that ΔΔG reliably depicts the selectivity trends in binary alloys reported for their high activity in the 2e-ORR. This analysis also enables the identification of nine selective 2e-ORR catalysts underscoring the efficacy of ΔΔG as 2e-ORR selectivity descriptor. This work highlights the significance of concurrently considering both selectivity and activity trends. This holistic approach is crucial for obtaining a comprehensive understanding in the identification of high-performance catalyst materials for optimal efficiency in various applications.

Study on Influence Factors of H2O2 Generation Efficiency on Both Cathode and Anode in a Diaphragm-Free Bath.

Electrosynthesis of H2O2 via both pathways of anodic two-electron water oxidation reaction (2e-WOR) and cathodic two-electron oxygen reduction reaction (2e-ORR) in a diaphragm-free bath can not only improve the generation rate and Faraday efficiency (FE), but also simplify the structure of the electrolysis bath and reduce the energy consumption. The factors that may affect the efficiency of H2O2 generation in coupled electrolytic systems have been systematically investigated. A piece of fluorine-doped tin oxide (FTO) electrode was used as the anode, and in this study, its catalytic performance for 2e-WOR in Na2CO3/NaHCO3 and NaOH solutions was compared. Based on kinetic views, the generation rate of H2O2 via 2e-WOR, the self-decomposition, and the oxidative decomposition rate of the generated H2O2 during electrolysis in carbonate electrolytes were investigated. Furthermore, by choosing polyethylene oxide-modified carbon nanotubes (PEO-CNTs) as the catalyst for 2e-ORR and using its loaded electrode as the cathode, the coupled electrolytic systems for H2O2 generation were set up in a diaphragm bath and in a diaphragm-free bath. It was found that the generated H2O2 in the electrolyte diffuses and causes oxidative decomposition on the anode, which is the main influent factor on the accumulated concentration in H2O2 in a diaphragm-free bath.

Roles of Oxygen-Containing Functional Groups in Carbon for Electrocatalytic Two-Electron Oxygen Reduction Reaction.

Recent years have witnessed great research interests in developing high-performance electrocatalysts for the two-electron (2e-) oxygen reduction reaction (ORR) that enables the sustainable and flexible synthesis of H2O2. Carbon-based electrocatalysts exhibit attractive catalytic performance for the 2e- ORR, where oxygen-containing functional groups (OFGs) play a decisive role. However, current understanding is far from adequate, and the contribution of OFGs to the catalytic performance remains controversial. Therefore, a critical overview on OFGs in carbon-based electrocatalysts toward the 2e- ORR is highly desirable. Herein, we go over the methods for constructing OFGs in carbon including chemical oxidation, electrochemical oxidation, and precursor inheritance. Then we review the roles of OFGs in activating carbon toward the 2e- ORR, focusing on the intrinsic activity of different OFGs and the interplay between OFGs and metal species or defects. At last, we discuss the reasons for inconsistencies among different studies, and personal perspectives on the future development in this field are provided. The results provide insights into the origin of high catalytic activity and selectivity of carbon-based electrocatalysts toward the 2e- ORR and would provide theoretical foundations for the future development in this field.

AC-electrochemical synthesis of H2O2 by breathing O2 in three-phase interface

Conventional electrosynthesis of H2O2 through a two-electron oxygen reduction reaction (2e− ORR) requires continuous O2 feeding as the reactant, which is produced by oxygen evolution reaction (OER) in water electrolysis. In principle, H2O2 can be directly synthesized from water once the 2e− ORR is coupled with OER in one electrode. Unfortunately, such effective coupling has not yet been established. Herein, we created a cyclic oxygen exhalation-inhalation for on-demand and on-site H2O2 production by coupling the OER and 2e− ORR with a facile alternating-current (AC) electrocatalytic process. By ingeniously manipulating the reaction interfaces and operating voltage, we achieved efficient and stable in-situ H2O2 production. The rapid oxygen transfer in the localized three-phase interface favors the sufficient electrochemical reactions. The AC-electrocatalytic system exhibits highest performance including H2O2 production rate of 90.16mmolh-1 gcat-1. Moreover, such AC-electrocatalysis inspires a new strategy to combine multiple electrocatalytic reactions into one electrode for fundamental study and practical applications.

Sulfur poisoned PtNi/C catalysts toward two-electron oxygen reduction reaction for acidic electrosynthesis of hydrogen peroxide

Selective electrocatalysis of two-electron oxygen reduction reaction (2e– ORR) has been recognized as a sustainable and on-site process for hydrogen peroxide (H2O2) production. Great progress has been achieved for 2e– ORR in alkaline media. However, it is challenged by insufficient activity and selectivity of the catalysts in acidic electrolytes. Herein, we report sulfur-poisoned PtNi/C catalysts (PtNiSx/C) that could regulate ORR from the 4e– to 2e– pathway. The identified PtNiS0.6/C offers high activity in terms of onset potential of ∼0.69 V (vs. RHE) and ∼80% selectivity. The mass activity is also comparable and outperforms representative Pt-based precious and transition-metal-based catalysts. In addition, it is interestingly found that the Faradaic efficiency further increased to 95% during the long-term electrolysis test due to Ni atom surface migration. The electrochemical production of the H2O2 system was applied to the electro-Fenton process, which has realized the effective degradation of organic pollutants in wastewater. This work offers a strategy by sulfur poisoning PtNi/C catalyst to realize Pt-based 2e– ORR active catalysts to electrolysis of H2O2 in acidic media.

Mechanism insights into H2O2in situ generation and activation for ciprofloxacin degradation by electro-peroxidation using the ACF@RuO2/Ti cathode

Electrocatalytic H2O2 production via the two-electron oxygen reduction reaction on the cathode surface plays a crucial role in the electro-peroxidation (EO-H2O2). In this work, the H2O2 generation potential of the EO-H2O2 process using an activated carbon fiber attached RuO2/Ti cathode (ACF@RuO2/Ti) was evaluated by simulation experiments with a high-precision syringe pump. Results shown that the actual average H2O2 accumulation rate reached up to 4.92 mg h−1 cm−2, while more than 95 % of the electrogenerated H2O2 was decomposed quickly. Electron paramagnetic resonance and quenching tests confirmed that the primary oxidant •OH was produced from H2O2 activation by ACF, RuO2 catalyst and their synergistic effect, while RuO2 played dominant role. The production of •OH in the EO-H2O2 process was also confirmed by the degradation and mineralization of antibiotic ciprofloxacin. The characterization results indicated that heterogeneous catalysis of cathode was due to both the pyridinic nitrogen and oxygen-containing groups of ACF, along with RuO2 catalyst on the RuO2/Ti surface. This study provides new insights into the mechanisms of the in situ H2O2 generation and activation in the EO-H2O2 process.

Magnetic field-enhanced oxygen reduction reaction for electrochemical hydrogen peroxide production with different cerium oxide nanostructures

We investigated cerium oxide nanoparticles of various morphologies (nanosheets, nanocubes, and nanoparticles) supported on carbon Vulcan XC-72 for the two-electron oxygen reduction reaction (ORR). A continuous magnetic field (2000 Oe) was used for the first time in the literature. The best results were for 5 % (w/w) CeO2 for all three different morphologies, more than doubling the ring current, enhancing the hydrogen peroxide selectivity from 51 % (Vulcan XC-72) to 84–89 %, and modifying the onset potential to lesser negative values. The presence of the magnetic field led to even higher ring currents with 5 % (w/w) CeO2, H2O2 selectivity from 54 % (Vulcan XC-72) to 88–96 % and changing even more the onset potential. Those results were correlated with the Zeeman effect, the Lorentz force, generating magnetohydrodynamic effects, the Kelvin force, and the formation of Bound Magnetic Polarons. This pioneering research introduces an innovative approach, highlighting the potential of an external continuous magnetic field.

N-coordinated Ag sites on ordered mesoporous carbons for highly efficient electrolytic production of H2O2 in acidic electrolyte

N-coordinated Ag (Ag-Nx) sites embedded in ordered mesoporous carbon (Ag-Nx/C) were prepared by pyrolyzation of Ag-2, 2-bipyridine complexes in the confined channels of mesoporous SBA-15 silica. This nanocasting method allowed high dispersion state of Ag-Nx sites on carbons with ordered mesoporous channels and higher specific surface area. Ag-Nx/C was found to be very active electrocatalyst for two-electron oxygen reduction reaction (2e- ORR) in 0.1 M HClO4 acidic electrolyte. The bulk electrolytic production for hydrogen peroxides (H2O2) could be achieved with a high production rate of 1.67 mol h−1 gcat−1 together with high electrolysis Faraday efficiency of about 93%. Ag-Nx/C also revealed better acid-resistant durability during H2O2 electrolysis production. This work provided an efficient and durable Ag-Nx/C electrocatalyst for electrolytic H2O2 production in acids.

Selective oxygen-doping in self-supportive carbon electrode by electrochemical oxidation for electrocatalytic synthesis of hydrogen peroxide

We report the selective introduction of oxygen-containing functional groups for two-electron oxygen reduction reaction (2e-ORR) in self-supportive carbon electrode using electrochemical oxidation method. The optimal electrode shows hydrogen peroxide (H2O2) selectivity up to 95 %. CO is found active to control 2e-ORR selectivity and mechanism of oxygen species variation is elucidated by in situ infrared reflection absorption spectroscopy. We further improve mass transfer by introducing highly interconnected macropores in electrode, which shows H2O2 yield of 144 mmol cm−2 h−1 and Faradaic efficiency of nearly 100 %. These may inspire advanced active electrode creation for applications through selective electrochemical doping and structural design.

Construction of integrated oxygen-rich carbon-based metal-free cathode to simultaneous boost wastewater treatment performance and energy recovery in bio-electro-Fenton system

Fenton coupled microbial fuel cells (MFCs) used for antibiotic pollution purification are limited by energy recovery and metal leakage of electrode. Here, we constructed a two-compartment bio-electro-Fenton (MFC-Fenton) with biological anode and Fenton cathode, which using carbon nanotube based on carbon brushes (OCNT-80/CB) with active centers rich in oxygen-containing functional groups as metal-free cathode. The results show that C = O locked environmental oxygen in the cathode can in-situ use the electrons produced by the anode through two-electron oxygen reduction reaction (2e− ORR) synthesize H2O2. •OH is further generated under activation of H2O2, achieving effective degradation of tetracycline (TC) in the cathode chamber. This study breaks through the limitations of poor pH adaptability and environmental secondary pollution caused by metal dissolution. Moreover, with the advantageous features of oxygen-containing functional groups active centers, good conductivity, and cyclic stability, the OCNT-80/CB achieves a maximum power density increased by 79.4 % as compared to that of the CB control. More notably, Microbial analysis further indicated that OCNT-80/CB electrode could simultaneously enhance Proteobacteria and Firmicutes abundance in bioanode. Dominant bacteria can self-metabolize environmental wastewater generate and recycle green energy. This study proved that careful structural design of cathode could promote the electrode performance. MFC-Fenton can be a competitive technology to enhance wastewater treatment and energy recovery simultaneously.

Preparation of nitrogen-doped carbon pyrolyzed from ZIF-8 and its performance in electrocatalytic oxygen reduction to hydrogen peroxide

As an environment-friendly strategy, electrocatalytic hydrogen peroxide (H2O2) generation via two-electron oxygen reduction reaction (2e– ORR) has attracted significant scientific and technological attention. Nevertheless, limited to the low catalytic activity and high cost of noble metal-containing catalysts, forging desired electrocatalysts with high catalytic activity, low cost, and sustainability is still challenging. In this work, nitrogen doped porous carbon materials named p-ZIF-800 and p-ZIF-950 were obtained by pyrolysis of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals at 800 °C and 950 °C, respectively. Then, they were employed as a catalytic layer in the gas diffusion electrodes p-ZIF-n/Ni/CB (n = 800 °C or 950 °C, CB = acetylene black). The production rates of H2O2 are up to 1.18 mg h−1 cm−2 and 1.25 mg h−1 cm−2 for p-ZIF-800/Ni/CB and p-ZIF-950/Ni/CB, respectively. Noticeably, although p-ZIF-800 had a lower degree of graphitization the difference in catalytic activity between p-ZIF-800 and p-ZIF-950 is negligible. This can be construed as a higher total nitrogen and richer mesoporous structure in p-ZIF-800 than in p-ZIF-950. Under optimized conditions of an electrode spacing of 3 cm, a pH value of 6.5, and a current density of 7.5 mA cm−2, the H2O2 production rate of p-ZIF-800/Ni/CB in the “floating-cathode” cell is up to as high as 2.09 mg h−1 cm−2, which is about 3.3 times higher than that of the cell with the “submerged-cathode” under aeration and stirring. Also, the p-ZIF-800/Ni/CB cathode demonstrates remarkable stability, it maintains its structure without losing catalytic activity after 5 catalytic cycle experiments. These results indicate that the state-of-the-art pyrolysis-based nitrogen-doped porous carbon materials exhibit a high potential for the advanced electrocatalyst of H2O2 electrogeneration.

B–F dual-doped carbon nanotubes for multi-site and high-rate two-electron oxygen reduction reaction electrocatalysis

Electrocatalytic two-electron oxygen reduction reaction (2e−-ORR) to produce hydrogen peroxide (H2O2) is a promising green way to replace the conventional anthraquinone reaction. Non-metallic catalysts are considered as low-cost catalysts due to their excellent stability and versatile surface chemistry. The performance of non-metallic electrocatalysts is usually limited by the limited catalytic active sites on the surface. Here, we report fluorine and boron dual-doped carbon nanotubes (B–F–C) as a metal-free electrocatalyst for H2O2 production, fabricated via a fast microwave treatment. With the synergistic effect of F and B, this strategy can effectively convert carbon and boron atoms on carbon nanotubes into highly active sites. As a result, an H2O2 yield up to 24.3 mol g−1 L−1 is achieved over B–F–C with a stable selectivity of above 90% within 0.2–0.7 V vs. RHE in 0.1 M KOH. Density functional theory (DFT)calculations further confirm that the multiple active sites created by the dual doping of fluorine and boron are the key factor in improving the performance of 2e−-ORR electrocatalysis. Therefore, this work offers a promising prospect for the design and preparation of catalysts with high catalytic activity for H2O2 production and other catalytic areas of industrial significance.

Cation Effects on the Acidic Oxygen Reduction Reaction at Carbon Surfaces.

Hydrogen peroxide (H2O2) is a widely used green oxidant. Until now, research has focused on the development of efficient catalysts for the two-electron oxygen reduction reaction (2e- ORR). However, electrolyte effects on the 2e- ORR have remained little understood. We report a significant effect of alkali metal cations (AMCs) on carbons in acidic environments. The presence of AMCs at a glassy carbon electrode shifts the half wave potential from -0.48 to -0.22 VRHE. This cation-induced enhancement effect exhibits a uniquely sensitive on/off switching behavior depending on the voltammetric protocol. Voltammetric and in situ X-ray photoemission spectroscopic evidence is presented, supporting a controlling role of the potential of zero charge of the catalytic enhancement. Density functional theory calculations associate the enhancement with stabilization of the *OOH key intermediate as a result of locally induced field effects from the AMCs. Finally, we developed a refined reaction mechanism for the H2O2 production in the presence of AMCs.

Engineering Co-N-Cr Cross-Interfacial Electron Bridges to Break Activity-Stability Trade-Off for Superdurable Bifunctional Single Atom Oxygen Electrocatalysts.

Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts have exhibited encouraging oxygen reduction reaction (ORR) activity. Nevertheless, the insufficient long-term stability remains a widespread concern owing to the inevitable 2-electron byproducts, H2O2. Here, we construct Co-N-Cr cross-interfacial electron bridges (CIEBs) via the interfacial electronic coupling between Cr2O3 and Co-N-C, breaking the activity-stability trade-off. The partially occupied Cr 3d-orbitals of Co-N-Cr CIEBs induce the electron rearrangement of CoN4 sites, lowering the Co-OOH* antibonding orbital occupancy and accelerating the adsorption of intermediates. Consequently, the Co-N-Cr CIEBs suppress the two-electron ORR process and approach the apex of Sabatier volcano plot for four-electron pathway simultaneously. As a proof-of-concept, the Co-N-Cr CIEBs is synthesized by the molten salt template method, exhibiting dominant 4-electron selectively and extremely low H2O2 yield confirmed by Damjanovic kinetic analysis. The Co-N-Cr CIEBs demonstrates impressive bifunctional oxygen catalytic activity (▵E=0.70 V) and breakthrough durability including 100 % current retention after 10 h continuous operation and cycling performance over 1500 h for Zn-air battery. The hybrid interfacial configuration and the understanding of the electronic coupling mechanism reported here could shed new light on the design of superdurable M-N-C catalysts.

In Situ Generation of H2O2 over MoOx Decorated on Cu2O@CuO Core-Shell Particle Nanoarchitectonics for Boosting Photocatalytic Oxidative Desulfurization.

Photocatalytic oxidation desulfurization (PODS) has emerged as a promising, ecofriendly alternative to traditional, energy-intensive fuel desulfurization methods. Nevertheless, its progress is still hindered due to the slow sulfide oxidation kinetics in the current catalytic systems. Herein, we present a MoOx decorated on a Cu2O@CuO core-shell catalyst, which enables a new, efficient PODS pathway by in situ generation of hydrogen peroxide (H2O2) with saturated moist air as the oxidant source. The photocatalyst delivers remarkable specific activity in oxidizing dibenzothiophene (DBT), achieving a superior rate of 7.8 mmol g-1 h-1, while maintaining a consistent performance across consecutive reuses. Experimental investigations reveal that H2O2 is produced through the two-electron oxygen reduction reaction (ORR), and both H2O2 and the hydroxyl radicals (•OH) generated from it act as the primary reactive species responsible for sulfide oxidation. Importantly, our catalyst accomplishes complete PODS of real diesel fuel, underscoring an appealing industrial prospect for our photocatalyst.