Electrochemical Synthesis Of Hydrogen Peroxide Research Articles

A Computation-Guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two-Dimensional Conductive Metal-Organic Framework for Efficient H2O2 Electrosynthesis.

Electrochemical synthesis of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e--ORR) provides an alternative method to the energy-intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e--ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e--ORR-inactive sites that result in poor H2O2 production rate and efficiency. Herein, guided by first-principle predictions, a substrate-free and two-dimensional conductive metal-organic framework (Ni-TCPP(Co)), composed of CoN4 sites in porphine(Co) centers and Ni2O8 nodes, is designed as a multi-site catalyst for H2O2 electrosynthesis. The approperiate distance between the CoN4 and Ni2O8 sites in Ni-TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high-density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni-TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e--ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90 %/85 % H2O2 selectivity within 0-0.8 V vs. RHE and >18.2/18.0 mol g-1 h-1 H2O2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high-density active sites, promoting high-efficiency electrosynthesis of H2O2 and beyond.

Tandem Oxidation Activation of Carbon for Enhanced Electrochemical Synthesis of H2O2: Unveiling the Role of Quinone Groups and Their Operando Derivatives

AbstractOxygen‐doped carbon materials show great promise to catalyze two‐electron oxygen reduction reaction (2e‐ORR) for electrochemical synthesis of hydrogen peroxide (H2O2), but the identification of the active sites is the subject of ongoing debate. In this study, a tandem oxidation strategy is developed to activate carbon black for achieving highly efficient electrochemical synthesis of H2O2. Acetylene black (AB) is processed with O2 plasma and subsequent electrochemical oxidation, resulting in a remarkable selectivity of >96% over a wide potential range, and a record‐setting high yield of >10 mol gcat−1 h−1 with good durability in gas diffusion electrode. Comprehensive characterizations and calculations revealed that the presence of abundant C═O groups at the edge sites positively correlated to and accounted for the excellent 2e‐ORR performance. Notably, the edge hydroquinone group formed from quinone under operando conditions, which is overlooked in previous research, is identified as the most active catalytic site.

Fragmented Polymetric Carbon Nitride with Rich Defects for Boosting Electrochemical Synthesis of Hydrogen Peroxide in Alkaline and Neutral Media.

Electrocatalytic oxygen reduction reaction via 2e- pathway is a safe and friendly route for hydrogen peroxide (H2O2) synthesis. In order to achieve efficient synthesis of H2O2, it is essential to accurately control the active sites. Here, fragmented polymetric carbon nitride with rich defects (DCN) is designed for H2O2 electrosynthesis. The multi-type defects, including the sodium atom doping in six-fold cavities, the boron atom doping at N-B-N sites and the cyano groups, are successfully created. Owing to the synergistic effect of these defects, the fragmented DCN achieves a high H2O2 production rateof 2.28 mol gcat. -1 h-1 and a high Faradic efficiency of nearly 90 % in alkaline media at 0.4 V vs. RHE in H-type cell. In neutral media, the H2O2 concentration produced by DCN can reach 1815 μM within 6 h at a potential of 0.2 V vs. RHE, and the H2O2 production rate of DCN is 0.23 mol gcat. -1 h-1. In addition, DCN shows excellent long-term durability in alkaline and neutral media. This study provides a new approach for the development of the boron, nitrogen doped carbon-based electrocatalysts for H2O2 electrochemical synthesis.

Metal Atom-Support Interaction in Single Atom Catalysts toward Hydrogen Peroxide Electrosynthesis.

Single metal atom catalysts (SACs) have garnered considerable attention as promising agents for catalyzing important industrial reactions, particularly the electrochemical synthesis of hydrogen peroxide (H2O2) through the two-electron oxygen reduction reaction (ORR). Within this field, the metal atom-support interaction (MASI) assumes a decisive role, profoundly influencing the catalytic activity and selectivity exhibited by SACs, and triggers a decade-long surge dedicated to unraveling the modulation of MASI as a means to enhance the catalytic performance of SACs. In this comprehensive review, we present a systematic summary and categorization of recent advancements pertaining to MASI modulation for achieving efficient electrochemical H2O2 synthesis. We start by introducing the fundamental concept of the MASI, followed by a detailed and comprehensive analysis of the correlation between the MASI and catalytic performance. We describe how this knowledge can be harnessed to design SACs with optimized MASI to increase the efficiency of H2O2 electrosynthesis. Finally, we distill the challenges that lay ahead in this field and provide a forward-looking perspective on the future research directions that can be pursued.

Elucidating the role of S-containing structure in carbon-based catalysts towards efficient H2O2 synthesis in seawater

The on-site sustainable electrochemical synthesis of hydrogen peroxide (H2O2) in natural seawater holds significant practical value in the fields of energy storage and environmental treatment. However, the poisoning of the active sites by ions such as Cl−, Ca2+, and Mg2+ in natural seawater significantly inhibits the ORR activity of the catalyst. Herein, the 2e− ORR performance of S, N co-doped carbon materials in natural seawater was investigated, focusing on the anti-Ca2+/Mg2+ poisoning mechanism of S-doped carbon structures. The data indicate a Faradaic efficiency of 94.2 % for H2O2 production, with a yield of 3.52 mol/(gcat h), and an approximate 100 % sterilization of bacteria and inactivation of chlorella within 10 min. S-doped carbon structures demonstrated enhanced H2O adsorption and dissociation properties during the ORR process, optimized the micro-environment of the catalytic interface, effectively inhibited Ca2+ and Mg2+ deposition. Moreover, S-doping altered the N coordination structure, further enhancing the 2e− ORR selectivity of the catalyst. This study demonstrates the high selectivity of 2e− ORR in natural seawater, offering guidance for designing catalysts using in the complex environment and advancing marine energy storage and environmental treatment technologies.

A novel naturally aspirated cathode for efficient electrosynthesis of hydrogen peroxide and wastewater purification in electro-Fenton systems

Electrochemical synthesis of hydrogen peroxide (H2O2) has developed rapidly in recent years as an alternative process to the anthraquinone method. However, the low H2O2 production and high energy consumption limit its further application. In this study, we propose a simple method to fabricate a naturally aspirated cathode (NAC), which significantly reduces the mass transfer resistance of oxygen and achieves a high oxygen diffusion coefficient (7.11 × 10-6 m2 s−1) and oxygen utilization efficiency (39.6 %). Additionally, the NAC provides a high density of reaction sites to achieve efficient production of H2O2 (0–84.33 mg h−1 cm−2) at near industrial current densities (0–240 mA cm−2) without external aeration. Meanwhile, the prepared NAC can degrade over 97.5 % of dyes within 10 min during the electro-Fenton process. The NAC exhibits excellent H2O2 production performance and great stability during long-term operation, which offers huge potential for industrial-scale electrochemical H2O2 production and the advanced oxidation processes (AOP) derived from it.

Effects of porous structure and oxygen functionalities on electrochemical synthesis of hydrogen peroxide on ordered mesoporous carbon

Two-electron oxygen reduction reaction (2e− ORR) is a promising alternative to energy-intensive anthraquinone process for hydrogen peroxide (H2O2) production. Metal-free nanocarbon materials have garnered intensive attention as highly prospective electrocatalysts for H2O2 production, and an in-depth understanding of their porous structure and active sites have become a critical scientific challenge. The present research investigates a range of porous carbon catalysts, including non-porous, microporous, and mesoporous structures, to elucidate the impacts of porous structures on 2e− ORR activity. The results highlighted the superiority of mesoporous carbon over other porous materials, demonstrating remarkable H2O2 selectivity. Furthermore, integration of X-ray photoelectron spectroscopy (XPS) data analysis with electrochemical assessment results unravels the moderate surface oxygen content is the key to increase 2e− ORR activity. These results not only highlight the intricate interplay between pore structure and oxygen content in determining catalytic selectivity, but also enable the design of carbon catalysts for specific electrochemical reactions.

S, N, and O tri-doped graphite nanosheets-based gas diffusion electrode boosts highly selective electrosynthesis of H2O2

Electrochemical synthesis of hydrogen peroxide (H2O2) via oxygen reduction reaction (ORR) is a promising environmentally friendly approach for on-site production of H2O2. The development of economically feasible cathodes with high activity and selectivity is of utmost importance to enable the large-scale application of the process of H2O2 electrosynthesis. Herein, a novel electrocatalyst of sulfur, nitrogen, and oxygen tri-doped graphite nanosheets (SNOGNSs) was developed, which exhibited the selectivity of up to 97.4 % for the electrosynthesis of H2O2, significantly higher than that of flake graphite (FG, 51.4 %), OGNSs (72.8 %) and NOGNSs (90.9 %). The gas diffusion electrode (GDE) was fabricated using SNOGNSs as catalysts, and the accumulation of H2O2 reached 732.8–1044.4 mg/Lh−1 at 0.3–0.5 A electrolytic current. The mechanism of the synergistic enhancement of two-electron ORR by S, N, and O tri-doping was revealed utilizing density functional theory (DFT) calculations. This work offers a suitable alternative for on-site clean production of H2O2 that can be applied in electrochemical advanced oxidation processes.

New and Revised Aspects of the Electrochemical Synthesis of Hydrogen Peroxide: From Model Electrocatalytic Systems to Scalable Materials

New and Revised Aspects of the Electrochemical Synthesis of Hydrogen Peroxide: From Model Electrocatalytic Systems to Scalable Materials

B, S co-doped mesoporous carbon as an efficient catalyst for H2O2 electrosynthesis in natural seawater

The small-scale electrochemical synthesis of hydrogen peroxide (H2O2) in marine environments is of great significance for environmental wastewater treatment, and the design of electrocatalysts for complicated marine conditions is the key for this technology. Although B-doped carbon materials have been demonstrated to be resistant to Cl− poisoning, the deposition of Ca2+ on the surface of catalyst in seawater and the sluggish reaction kinetics of non-metallic catalysts remain to be solved. Herein, B, S co-doped mesoporous carbon materials were synthesized by a simple NaCl template method. The H2O2 yield of the as-prepared sample was up to 3.66 mol/(gcat h) with a Faradaic Efficiency (FE) of 97.98 % at 100 mA/cm2 in natural seawater, and achieved 100 % inactivation of bacteria and Chlorella within 5 min at a low current density. Based on the structural characterization and electrochemical results, the S-containing structure on the carbon matrix suppresses Ca2+ deposition due to its excellent proton adsorption activity. Furthermore, the electron transfer process between the reactant and BC3 was enhanced by the abundant mesoporous structure, so as to optimize the sluggish oxygen reduction reaction (ORR) kinetics on BC3. This work offers a strategy for inactivation of marine microorganisms and the degradation of organic pollutants, which promotes the advancement of marine wastewater treatment technology, and also provides reference for the design of metal free catalysts used in marine environments.

Ni-doped sites in yeast-derived catalysts for efficient electrochemical synthesis of hydrogen peroxide

The electrochemical synthesis of hydrogen peroxide (H2O2) via the 2-electron pathway of oxygen reduction reaction offers a green and on-site product. However, there remains an urgent need to develop cost-efficient electrocatalysts with H2O2 productivity that meets practical industrial-scale requirements. In this study, yeast-derived carbon material loaded with multiple Ni active sites achieved electrochemical synthesis of H2O2 at industrial current density. The precursor of heteroatom-doped carbon material was obtained through high-dispersed Ni(II) adsorption on yeast cells. By adjusting the pyrolysis temperature and Ni loading dosage, the carbon framework, pore structure, and Ni active sites within the obtained Ni/yeast were successfully regulated. Ni/yeast featured with highly active Ni single-atom sites, metallic Ni nanoparticles and Ni2P nanoparticles, enabling stable running for 10 h at 200 mA cm−2 in a flow cell. Ni/yeast exhibits remarkable H2O2 Faradaic efficiency of 94.6 % and a yield of 35.3 mol gcat−1h−1. The abundant pore structure and multiple Ni active sites within Ni/yeast provide promising avenues for manipulating heteroatom-doped carbon materials in H2O2 electrosynthesis.

Strain-induced catalytic enhancement in Co-BTA and Rh-BTA for efficient 2e- oxygen reduction: a DFT study.

Here we design TM-BTA catalysts for the electrochemical synthesis of hydrogen peroxide (H2O2), focusing on the efficient two-electron (2e-) oxygen reduction pathway. Employing density functional theory (DFT), we screened 17 transition metals, identifying Co-BTA and Rh-BTA as outstanding candidates based on their low overpotentials and superior catalytic activity. A key innovation is the application of mechanical strain to these catalysts, significantly optimizing their performance by modulating the d-band center. This approach enhances the adsorption of oxygen-containing intermediates, crucial for the 2e- ORR process. Our findings demonstrate that a tensile strain of 1.95% optimally enhances catalytic efficiency in both Co-BTA and Rh-BTA, substantially reducing overpotential. This research not only highlights the potential of TM-BTA catalysts in H2O2 production but also underscores the importance of strain modulation as a cost-effective and efficient method to improve the selectivity and activity of electrocatalysts, offering a novel perspective in the field of sustainable chemical synthesis.

Coordination engineering regulating metal single-atom anchored on n-doped carbon as a bifunctional catalyst for H2O2 production via dual channels

Electrochemical synthesis of hydrogen peroxide (H2O2) via two-electron oxygen reduction reaction (2e- ORR) or two-electron water oxidation reaction (2e- WOR), parades great prospects in substituting traditional anthraquinone process. However, the low efficiency and selectivity hinders its practical utilization. Exploration of a bifunctional catalyst capable of simultaneously driving the 2e- WOR and 2e- ORR is crucial for thoroughly improving H2O2 conversion efficiency. Herein, by means of first principles calculation, the 2e- ORR and 2e- WOR activities of metal-nitrogen doped carbon (M−NC, M = Mn, Fe, Co, Ni, Ru, In, and Pt) are investigated. Combining the pyrrole nitrogen coordination regulation, the best sample (RuN(Po)4) is screened from forty single atom configurations, which exhibits ultra-low overpotentials (0.02 V/0.04 V) and excellent inhibition on 4e- ORR/WOR side reactions. In-depth study further verifies its low reaction energy barrier and high thermodynamic stability for H2O2 synthesis in two pathways. Our work is expected to provide useful understanding for designing highly-efficient bifunctional catalysts for H2O2 production.

Perspectives on Carbon-Based Catalysts for the Two-Electron Oxygen Reduction Reaction for Electrochemical Synthesis of Hydrogen Peroxide: A Minireview

Perspectives on Carbon-Based Catalysts for the Two-Electron Oxygen Reduction Reaction for Electrochemical Synthesis of Hydrogen Peroxide: A Minireview

Platinum Single-Atom catalysts confined in NH2-UIO-66 for highly selective oxygen reduction reaction

The electrochemical synthesis of hydrogen peroxide via the two-electron oxygen reduction reaction (2e–ORR) offers a green and environment-friendly production method. Here, Pt single-atom catalyst confined in NH2-UIO-66 was successfully prepared by glow discharge plasma at room temperature, and it was used for the 2e–ORR. The plasma treated sample exhibited a high H2O2 selectivity of 99.86%, surpassing that of the samples prepared by calcination and chemical reduction methods. NH2-UIO-66 inhibits the growth of Pt particles and improves Pt dispersion. Plasma prevents Pt aggregation due to the low temperature and enhances the interaction between Pt and NH2-UIO-66 which leads to an outstanding electrocatalytic ORR. This work provides strategies towards single-atom catalysts through the confinement of metal–organic frameworks for electrocatalysis.

Mimicking Metalloenzyme Microenvironments in the Transition Metal-Single Atom Catalysts for Electrochemical Hydrogen Peroxide Synthesis in an Acidic Medium.

Electrochemical reduction of oxygen into hydrogen peroxide in an acidic medium offers an energy-efficient and green H2 O2 synthesis as an alternative to the energy-intensive anthraquinone process. Unfortunately, high overpotential, low production rates, and fierce competition from traditional four-electron reduction limit it. In this study, a metalloenzyme-like active structure is mimicked in carbon-based single-atom electrocatalysts for oxygen reduction to H2 O2 . Using a carbonization strategy, the primary electronic structure of the metal center with nitrogen and oxygen coordination is modulated, followed by epoxy oxygen functionalities close to the metal active sites. In an acidic medium, CoNOC active structures proceed with greater than 98% H2 O2 selectivity (2e- /2H+ ) rather than CoNC active sites that are selective to H2 O (4e- /4H+ ). Among all MNOC (M=Fe, Co, Mn, and Ni) single-atom electrocatalysts, the CoNOC is the most selective (> 98%) for H2 O2 production, with a mass activity of 10Ag-1 at 0.60V vs. RHE. X-ray absorption spectroscopy is used to identify the formation of unsymmetrical MNOC active structures. Experimental results are also compared to density functional theory calculations, which revealed that the structure-activity relationship of the epoxy-surrounded CoNOC active structure reaches optimum (ΔG*OOH ) binding energies for high selectivity.

Coherent Sub-Nanometer Interface between Crystalline and Amorphous Materials Boosts Electrochemical Synthesis of Hydrogen Peroxide.

There are enormous yet largely underexplored exotic phenomena and properties emerging from interfaces constructed by diverse types of components that may differ in composition, shape, or crystal structure. It remains poorly understood the unique properties a coherent interface between crystalline and amorphous materials may evoke, and there lacks a general strategy to fabricate such interfaces. It is demonstrated that by topotactic partial oxidation heterostructures composed of coherently registered crystalline and amorphous materials can be constructed. As a proof-of-concept study, heterostructures consisting of crystalline P3 N5 and amorphous P3 N5 Ox can be synthesized by creating amorphous P3 N5 Ox from crystalline P3 N5 without interrupting the covalent bonding across the coherent interface. The heterostructure is dictated by nanometer-sized short-range-ordered P3 N5 domains enclosed by amorphous P3 N5 Ox matrix, which entails simultaneously fast charge transfer across the interface and bicomponent synergistic effect in catalysis. Such a P3 N5 /P3 N5 Ox heterostructure attains an optimal adsorption energy for *OOH intermediates and exhibits superior electrocatalytic performance toward H2 O2 production by adopting a selectivity of 96.68% at 0.4 VRHE and a production rate of 321.5 mmol h-1 gcatalyst -1 at -0.3 VRHE . The current study provides new insights into the synthetic strategy, chemical structure, and catalytic property of a sub-nanometer coherent interface formed between crystalline and amorphous materials.

Electrosynthesis of Hydrogen Peroxide through Selective Oxygen Reduction: A Carbon Innovation from Active Site Engineering to Device Design.

Electrochemical synthesis of hydrogen peroxide (H2 O2 ) through the selective oxygen reduction reaction (ORR) offers a promising alternative to the energy-intensive anthraquinone method, while its success relies largely on the development of efficient electrocatalyst. Currently, carbon-based materials (CMs) are the most widely studied electrocatalysts for electrosynthesis of H2 O2 via ORR due to their low cost, earth abundance, and tunable catalytic properties. To achieve a high 2e- ORR selectivity, great progress is made in promoting the performance of carbon-based electrocatalysts and unveiling their underlying catalytic mechanisms. Here, a comprehensive review in the field is presented by summarizing the recent advances in CMs for H2 O2 production, focusing on the design, fabrication, and mechanism investigations over the catalytic active moieties, where an enhancement effect of defect engineering or heteroatom doping on H2 O2 selectivity is discussed thoroughly. Particularly, the influence of functional groups on CMs for a 2e- -pathway is highlighted. Further, for commercial perspectives, the significance of reactor design for decentralized H2 O2 production is emphasized, bridging the gap between intrinsic catalytic properties and apparent productivity in electrochemical devices. Finally, major challenges and opportunities for the practical electrosynthesis of H2 O2 and future research directions are proposed.

Spectroscopic Identification of Active Sites of Oxygen-Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide.

The electrochemical synthesis of hydrogen peroxide (H2 O2 ) via a two-electron (2 e- ) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst for H2 O2 electrochemical production. The optimized PCC900 material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2 O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.

Spectroscopic Identification of Active Sites of Oxygen‐Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide

AbstractThe electrochemical synthesis of hydrogen peroxide (H2O2) via a two‐electron (2 e−) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy‐intensive anthraquinone process. Herein, we develop a facile template‐protected strategy to synthesize a highly active quinone‐rich porous carbon catalyst for H2O2 electrochemical production. The optimized PCC900 material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron‐based near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e− ORR performance. The effectiveness of chair‐form quinone groups as the most efficient active sites is highlighted by the molecule‐mimic strategy and theoretical analysis.