Rate Of H2O2 Production Research Articles

Simultaneous photocatalytic hydrogen peroxide production and pollutant degradation via bipyridine-based polyimide covalent organic framework

Covalent organic framework (COF) photocatalysts for hydrogen peroxide (H2O2) production are receiving significant attention because of the ever-increasing demand for H2O2. Despite the redox-active property and notable photophysical characteristics of polyimide (PI), the potential of PI-based COFs (PICs) for photocatalytic H2O2 production remains unexplored. Herein, we present a dual redox-active bipyridine-containing PIC (PIC-BPY) as an efficient photocatalyst for H2O2 production. PIC-BPY demonstrated exceptional performance by achieving an H2O2 production rate of 2772 μmol gcat.−1, which is three times higher than its biphenyl-based counterpart. We elucidated the reaction pathway through a series of scavenger tests and electron spin resonance analysis, thereby confirming the additional active role of BPY along with that of PIC framework. Furthermore, we harnessed hydroxyl radicals generated during photocatalysis to explore the potential of PIC-BPY for concurrent pollutant degradation and H2O2 production.

Enhanced electroproduction of hydrogen peroxide with oxidized boron-doped carbon catalysts synthesized from gaseous CO2

As an eco-friendly alternative to the conventional anthraquinone process, electrochemical production of hydrogen peroxide (H2O2) through the oxygen reduction reaction has been attracting attention. The goal of this work is to derive a carbon-based material from carbon dioxide (CO2) to achieve high performance in electrochemical H2O2 production. Doping heterogeneous element such as oxygen on a carbon catalyst has been mainly explored to increase the selectivity and activity, but little research has been conducted on enhancing catalytic activity with oxidized boron insertion. This study proposes porous carbon materials synthesized from CO2 as electrocatalysts. Polyethylene oxide (PEO) was thermally treated together to increase the boron-oxygen bonding sites. As a result, the synthesized carbon materials having oxidized boron functional groups of BC2O and BCO2 showed high activity (1.25 mA cm−2) and selectivity (∼90 %) over a wide voltage range in two-electron ORR (Oxygen Reduction Reaction) at alkaline media. Furthermore, in an H-cell where 0.4 V vs. RHE was applied, the average H2O2 production rate was maintained at 452.96 mmol g−1 h−1 for four hours with a high faraday efficiency of 90 %.

Integrative Active Sites of Cathode for Electron-Oxygen-Proton Coupling To Favor H2O2 Production in a Photoelectrochemical System.

The oxygen reduction process generating H2O2 in the photoelectrochemical (PEC) system is milder and environmentally friendly compared with the traditional anthraquinone process but still lacks the efficient electron-oxygen-proton coupling interfaces to improve H2O2 production efficiency. Here, we propose an integrated active site strategy, that is, designing a hydrophobic C-B-N interface to refine the dearth of electron, oxygen, and proton balance. Computational calculation results show a lower energy barrier for H2O2 production due to synergistic and coupling effects of boron sites for O2 adsorption, nitrogen sites for H+ binding, and the carbon structure for electron transfer, demonstrating theoretically the feasibility of the strategy. Furthermore, we construct a hydrophobic boron- and nitrogen-doped carbon black gas diffusion cathode (BN-CB-PTFE) with graphite carbon dots decorated on a BiVO4 photoanode (BVO/g-CDs) for H2O2 production. Remarkably, this approach achieves a record H2O2 production rate (9.24 μmol min-1 cm-2) at the PEC cathode. The BN-CB-PTFE cathode exhibits an outstanding Faraday efficiency for H2O2 production of ∼100%. The newly formed h-BN integrative active site can not only adsorb more O2 but also significantly improve the electron and proton transfer. Unexpectedly, coupling BVO/g-CDs with the BN-CB-PTFE gas diffusion cathode also achieves a record H2O2 production rate (6.60 μmol min-1 cm-2) at the PEC photoanode. This study opens new insight into integrative active sites for electron-O2-proton coupling in a PEC H2O2 production system that may be meaningful for environment and energy applications.

Piezo-photocatalytic synergetic for H2O2 generation via dual-pathway over Z-scheme ZIF-L/g-C3N4 heterojunction

The constructed ZIF-L/g-C3N4 piezo-photocatalytic system showed exceptional H2O2 production yield. It was primarily attributable to the matched Z-scheme band alignments and the forceful piezoelectric field formed between g-C3N4 and ZIF-L, which was favor of reducing the energy barrier of electron excitation and directional transferring of photo-generated charge carriers. Meanwhile, the composition between ZIF-L and g-C3N4 can alter the H2O2 generation mechanism from single-pathway to dual-pathway. Thus, this mutual promotion significantly elevated the catalytic H2O2 production rate to 1.45 mmol g−1 h−1 without any contaminative scavenger. The catalytically produced H2O2 solution can be used to achieve ultrafast degradation of organic pollutants with 100% efficiency through homogeneous Fenton reaction within tens of seconds. The mediating multi-roles of natural organic matter (NOM) in regulating the H2O2 production were systematically investigated. Finite-element-method (FEM) simulations and density functional theory (DFT) calculations conjointly revealed the constructed piezo-photocatalytic system not only markedly accelerated separation of charge carriers, but also facilitated the activation of vital intermediates (O2*, OOH* and *OH) for H2O2 synthesis, which were the rate-determining steps for oxygen reduction reaction (ORR) and water oxidation reaction (WOR). This study will provoke the rational design of MOFs-based dual-pathway materials for piezo-photocatalytic H2O2 generation and follow-up applications.

Augmentation of physiology and productivity, and reduction of lead accumulation in lettuce grown in lead contaminated soil by rhizobacteria-assisted rhizoengineeing

Microbial-assisted rhizoengineering is a promising biotechnology for improving crop productivity. In this study, lettuce roots were bacterized with two lead (Pb) tolerant rhizobacteria including Pseudomonas azotoformans ESR4 and P. poae ESR6, and a consortium consisted of ESR4 and ESR6 to increase productivity, physiology and antioxidants, and reduce Pb accumulation grown in Pb-contaminated soil i.e., 80 (Pb in native soil), 400 and 800 mg kg−1 Pb. In vitro studies showed that these strains and the consortium produced biofilms, synthesized indole-3-acetic acid and NH3, and solubilized phosphate challenging to 0, 100, 200 and 400 mg L−1 of Pb. In static conditions and 400 mg L−1 Pb, ESR4, ESR6 and the consortium adsorbed 317.0, 339.5 and 357.4 mg L−1 Pb, respectively, while 384.7, 380.7 and 373.2 mg L−1 Pb, respectively, in shaking conditions. Fourier transform infrared spectroscopy results revealed that several functional groups [Pb–S, M − O, O–M–O (M = metal ions), S–S, PO, CO, –NH, –NH2, C–C–O, and C–H] were involved in Pb adsorption. ESR4, ESR6 and the consortium-assisted rhizoengineering (i) increased leaf numbers and biomass production, (ii) reduced H2O2 production, malondialdehyde, electrolyte leakages, and transpiration rate, (iii) augmented photosynthetic pigments, photosynthetic rate, water use efficiency, total antioxidant capacity, total flavonoid content, total phenolic content, and minerals like Ca2+ and Mg2+ in comparison to non-rhizoengineering plants grown in Pb-contaminated soil. Principal component analysis revealed that higher pigment production and photosynthetic rate, improved water use efficiency and increased uptake of Ca2+ were interlinked to increased productivity by bacterial rhizoengineering of lettuce grown in different levels of Pb exposures. Surprisingly, Pb accumulation in lettuce roots and shoots was remarkably decreased by rhizoengineering than in non-rhizoengineering. Thus, these bacterial strains and this consortium could be utilized to improve productivity and reduce Pb accumulation in lettuce.

Enhanced Electron Delocalization Induced by Ferromagnetic Sulfur doped C 3 N 4 Triggers Selective H 2 O 2 Production

For the 2D metal‐free carbon catalysts, the atomic coplanar architecture enables a large number of pz orbitals to overlap laterally, thus forming π‐electron delocalization, and the delocalization degree of the central atom dominates the catalytic activity. Herein, designing sulfur‐doped defect‐rich graphitic carbon nitride (S‐Nv‐C3N4) materials as a model, we propose a strategy to promote localized electron polarization by enhancing the ferromagnetism of ultra‐thin 2D carbon nitride nanosheets. The introduction of sulfur (S) further promotes localized ferromagnetic coupling, thereby inducing long‐range ferromagnetic ordering and accelerating the electron interface transport. Meanwhile, the hybridization of sulfur atoms breaks the symmetry and integrity of the unit structure, promotes electron enrichment and stimulating electron delocalization at the active site. This optimization enhances the *OOH desorption, providing a favorable kinetic pathway for the production of hydrogen peroxide (H2O2). Consequently, S‐Nv‐C3N4 exhibits high selectivity (>95%) and achieves a superb H2O2 production rate, approaching 4374.8 ppm during continuous electrolysis over 300‐hour. According to theoretical calculation and in‐situ spectroscopy, the ortho‐S configuration can provide ferromagnetic perturbation in carbon active centers, leading to the electron delocalization, which optimizes the OOH* adsorption during the catalytic process.

Hydrogen peroxide production in pure water on a pyrrole-containing hydrothermal carbon photocatalyst

Herein, a pyrrole-containing hydrothermal carbon (N-SHTC) was developed by a simple one-step hydrothermal carbonization approach using starch and nitric acid as starting reactants. The introduction of nitric acid promoted the dehydration and carbonization of starch and led to the synthesis of N-SHTC at lower hydrothermal temperature, and also resulted in the incorporation of N into the furan structure to form pyrrole units. The charge transfer efficiency of N-SHTC was significantly improved due to the introduced pyrrole units as potential electron acceptor. With no scavengers or O2 bubbling, N-SHTC exhibited a H2O2 production rate of 1132 μmol g−1 h−1 in pure water under visible light. Notably, the H2O2 photoproduction performance of N-SHTC was further enhanced in the presence of metal salt ions due to the strengthened electron-withdrawing property of pyrrole units caused by the metal salt ions. These merits enabled N-SHTC the potentially practical applications in photocatalytic production of H2O2.

Indium oxide-based Z-scheme hollow core–shell heterostructure with rich sulfur-vacancy for highly efficient light-driven splitting of water to produce clean energy

Crafting an inorganic semiconductor heterojunction with defect engineering and morphology modulation is a strategic approach to produce clean energy by the highly efficient light-driven splitting of water. In this paper, a novel Z-scheme sulfur-vacancy containing Zn3In2S6 (Vs-Zn3In2S6) nanosheets/In2O3 hollow hexagonal prisms heterostructrue (Vs-ZIS6INO) was firstly constructed by an oil bath method, in which Vs-Zn3In2S6 nanosheets grew on the surfaces of In2O3 hollow hexagonal prisms to form a hollow core–shell structure. The obtained Vs-ZIS6INO heterostructrue exhibited much enhanced activity of the production of H2 and H2O2 by the light-driven water splitting. In particular, under visible light irradiation (λ > 420 nm), the rate of generation of H2 of Vs-ZIS6INO sample containing 30 wt% Vs-Zn3In2S6 (30Vs-ZIS6INO) could reach 3721 μmol g–1h−1, which was 87 and 6 times higher than those of Zn3In2S6 (43 μmol g–1h−1) and Vs-Zn3In2S6 (586 μmol g–1h−1), respectively. Meanwhile, 30Vs-ZIS6INO could exhibit the rate of H2O2 production of 483 μmol g–1h−1 through the dual pathways of indirect 2e– oxygen reduction (ORR) and water oxidation (WOR) without adding any sacrifice agents, far exceeding In2O3 (7 μmol g–1h−1) and Vs-Zn3In2S6 (58 μmol g–1h−1). The excellent photocatalytic activities of H2 and H2O2 generations of Vs-ZIS6INO sample might result from the synergistic effect of the sulfur vacancy, hollow core–shell structure, and Z-scheme heterostructure, which accelerated the electron delocalization, enhanced the absorption and conversion of solar energy, reduced the carrier diffusion distance, and ensured high REDOX ability. In addition, the possible photocatalytic mechanisms for the production of H2 and H2O2 were discussed in detail. This study provided a new idea and reference for constructing the novel and efficient inorganic semiconductor heterostructures by coordinating vacancy defect and morphology design to adequately utilize water splitting for the production of clean energy.

Abundant Edge Active Sites-Modified High-Crystalline g-C3N5 for Hydrogen Peroxide Production from Pure-Water via a Quasi-Homogeneous Photocatalytic Process.

Ultrathin carbon nitride pioneered a paradigm that facilitates effective charge separation and acceleration of rapid charge migration. Nevertheless, the dissociation process confronts a disruption owing to the proclivity of carbon nitride to reaggregate, thereby impeding the optimal utilization of active sites. In response to this exigency, the adoption of a synthesis methodology featuring alkaline potassium salt-assisted molten salt synthesis is advocated in this work, aiming to craft a nitrogenated graphitic carbon nitride (g-C3N5) photocatalyst characterized by thin layer and hydrophilicity, which not only amplifies the degree of crystallization of g-C3N5 but also introduces a plethora of abundant edge active sites, engendering a quasi-homogeneous photocatalytic system. Under visible light irradiation, the ultra-high H2O2 production rate of this modified high-crystalline g-C3N5 in pure water attains 151.14µmh-1. This groundbreaking study offers a novel perspective for the innovative design of highly efficient photocatalysts with a quasi-homogeneous photocatalytic system.

Schottky Junction Enhanced Photosynthesis of Hydrogen Peroxide by Ultrathin Porous Carbon Nitride Supported Ni Nanoparticles.

Artificial photosynthesis for high-value hydrogen peroxide (H2O2) through a two-electron reduction reaction is a green and sustainable strategy. However, the development of highly active H2O2 photocatalysts is impeded by severe carrier recombination, ineffective active sites, and low surface reaction efficiency. We developed a dual optimization strategy to load dense Ni nanoparticles onto ultrathin porous graphitic carbon nitride (Ni-UPGCN). In the absence and presence of sacrificial agents, Ni-UPGCN achieved H2O2 production rates of 169 and 4116 μmol g-1 h-1 with AQY (apparent quantum efficiency) at 420 nm of 3.14% and 17.71%. Forming a Schottky junction, the surface-modified Ni nanoparticles broaden the light absorption boundary and facilitate charge separation, which act as active sites, promoting O2 adsorption and reducing the formation energy of *OOH (reaction intermediate). This results in a substantial improvement in both H2O2 generation activity and selectivity. The Schottky junction of dual modulation strategy provides novel insights into the advancement of highly effective photocatalytic agents for the photosynthesis of H2O2.

Atomically dispersed asymmetric cobalt electrocatalyst for efficient hydrogen peroxide production in neutral media

Electrochemical hydrogen peroxide (H2O2) production (EHPP) via a two-electron oxygen reduction reaction (2e- ORR) provides a promising alternative to replace the energy-intensive anthraquinone process. M-N-C electrocatalysts, which consist of atomically dispersed transition metals and nitrogen-doped carbon, have demonstrated considerable EHPP efficiency. However, their full potential, particularly regarding the correlation between structural configurations and performances in neutral media, remains underexplored. Herein, a series of ultralow metal-loading M-N-C electrocatalysts are synthesized and investigated for the EHPP process in the neutral electrolyte. CoNCB material with the asymmetric Co-C/N/O configuration exhibits the highest EHPP activity and selectivity among various as-prepared M-N-C electrocatalyst, with an outstanding mass activity (6.1 × 105 A gCo−1 at 0.5 V vs. RHE), and a high practical H2O2 production rate (4.72 mol gcatalyst−1 h−1 cm−2). Compared with the popularly recognized square-planar symmetric Co-N4 configuration, the superiority of asymmetric Co-C/N/O configurations is elucidated by X-ray absorption fine structure spectroscopy analysis and computational studies.

Synergistic selenium doping and colloidal quantum dots decoration over ZnIn2S4 enabling high-efficiency photoelectrochemical hydrogen peroxide production

Photoelectrochemical (PEC) water splitting to value-added hydrogen peroxide (H2O2) production is more promising than the traditional O2 evolution. However, enabling efficient PEC H2O2 generation is still challenging due to competitive two-/four-electron water oxidation pathways. In this work, ZnIn2S4 (ZIS) photoanodes were engineered by Se doping and colloidal quantum dots (QDs) modification to boost the PEC H2O2 evolution efficiency. Morphology and elemental studies testify the successful Se doping in ZIS and the anchoring of QDs on ZIS-Se photoelectrodes. Photoinduced carrier kinetics investigation verifies the optimized band bending, suppressed charge recombination, and promoted charge transfer in as-prepared ZIS-Se and ZIS-Se/QDs photoanodes, exhibiting inhibited four-electron O2 evolution and facilitated two-electron H2O2 production during PEC water oxidation, as evidenced by the density functional theory (DFT) calculations. Accordingly, the Se-doped and QDs-decorated ZIS photoelectrodes demonstrate a gradually less upward band bending and improved photo-excited hole transfer to the surface, delivering a maximum H2O2 production rate of 1.32 μmol min−1 cm−2 with a Faraday efficiency of 86 % at 1.23 V versus reversible hydrogen electrode (RHE) under one sun illumination.

Accelerated sonochemical fabrication of MIn2S4 (M = Zn, Mg, Ni, Co) for ultra-high photocatalytic hydrogen peroxide production

Ternary metal sulfide (MIn2S4) by virtue of large extinction coefficient, suitable band gap and stability, has been proposed as a candidate for photocatalytic synthesis hydrogen peroxide (H2O2). However, MIn2S4 is conventionally synthesized by solvothermal method that is generally characterized by tedious operational steps and long reaction time. In this work, four sonoMIn2S4 (M = Zn, Mg, Ni, Co) were successfully prepared by sonochemical method within 2 h. These as-synthesized sonoMIn2S4 delivered much high-efficient photocatalytic H2O2 generation. Particularly, the sonoZnIn2S4 presented H2O2 production rate of 21295.5 μmol∙g−1∙h−1 in water/benzylalcohol system, which is 3.0 times that of ZnIn2S4 prepared by solvothermal method. The remarkably improved photocatalytic performance of sonoZnIn2S4 might be due to the multiple defects and fast electron-hole pair separation caused by ultrasound cavitation effect. Other metal sulfide photocatalysts with high performance were efficiently fabricated by facile sonochemical technology as well. The sonochemical method realized the rapid preparation of metal sulfide photocatalysts and efficient production of H2O2, which benefits to meet the United Nations Sustainable Development Goals (SDGs) including SDG-7 and SDG-12.

Understanding the effect of multiple configurations in polymeric carbon nitride for efficient solar-driven hydrogen peroxide photosynthesis

A oxygen and potassium co-doped polymeric carbon nitride (O/K-PCNs) was simply constructed by an acid gas cutting strategy for photocatalytic H2O2 generation. The effect of each accompanied configurations on photosynthesis of H2O2 was systematically analyzed. The C–O–C structure formed by O doping is capable of decreasing K ions incorporated energy barrier, thus remarkably improving the content of crucial K active sites. Dual heteroatom sites synergistically enhance O2 adsorption and surface ORR by a bridge K–O–O–C model. Moreover, the accompanied cyano defect and poly(heptazine imide) is responsible for improving in-plane and interlayer carriers separation, respectively. The optimal O/K-PCNs exhibits 60-fold higher photocatalytic H2O2 production rate than pure PCN. A positive correlation between the H2O2 production rate and the K heteratoms content was established. This work clarifies role of multiple configurations in PCN, especially O-containing groups, providing a new insight for design heteroatoms-doped materials for solar energy conversion.

Towards highly-selective H2O2 photosynthesis: In-plane highly ordered carbon nitride nanorods with Ba atoms implantation

Graphitic carbon nitride (g-C3N4) shows great potential in photocatalytic H2O2 production. However, challenges arise from its low in-plane crystallinity and selectivity in two-electron oxygen reduction reaction (2e−-ORR), greatly limiting its H2O2 photosynthesis efficiency. Herein, we develop an ingenious strategy to simultaneously increase the in-plane crystallinity and induce the highly-selective 2e−-ORR by rationally designing barium (Ba) atom-implanted in-plane highly ordered g-C3N4 nanorods. The approach involves controllable synthesis of in-plane high crystallinity g-C3N4 nanorods with Ba implantation (BI-CN) using a BaCl2-mediated in-plane polymerization strategy. The unique Ba-N interaction induces the oriented polymerization of 3-s-triazine units to form well-arranged in-plane structures. Experimental and theoretical calculations clarify that the implanted Ba atoms function as positive charge centers, resulting in a Pauling-type O2 adsorption configuration. This minimizes O–O bond breaking energy, thus suppressing the four-electron oxygen reduction reaction (4e−-ORR) and facilitating a highly-selective 2e−-ORR pathway for efficient photocatalytic H2O2 production. Consequently, the optimized BI-CN3 photocatalyst exhibits an outstanding H2O2 production rate of as high as 353 μmol L−1 h−1, surpassing the pristine g-C3N4 by 6.1 times. This study concurrently optimizes the in-plane crystallinity and O2 adsorption sites of g-C3N4 photocatalysts for highly-selective H2O2 production, providing innovative insights for designing efficient photocatalysts with diverse applications.

Regulation of d-band center of TiO2 through fluoride doping for enhancing photocatalytic H2O2 production activity

Titanium dioxide (TiO2) has received extensive attention for photocatalytic hydrogen peroxide (H2O2) production, with the d-band center related to the adsorption performance, which affects the photocatalytic reaction process. Herein, an ingenious strategy to lower the antibonding-orbital occupancy in the Ti 3d orbital by fluoride ion (F−) doping is proposed, with density functional theory calculations predicting that F-doping into TiO2 induces a non-uniform charge distribution and enables an upshift of the d-band center in F/TiO2. This manipulation provides accessible active centers with favorable d-band energy levels, which can improve the charge-transfer behavior, strengthen the interaction between the adsorbed oxygen and the photocatalyst, and reduce the adsorption energy of oxygen, eventually promoting the photocatalytic H2O2 production rate. The experimental results further confirm that a lower antibonding-orbital occupancy can intensify the adsorption of atomic oxygen at the Ti sites. Electron paramagnetic resonance experiment reveals that the presence of F− ions in the lattice induces the formation of Ti3+ centers that localize the extra electron needed for charge compensation. Femtosecond transient absorption (fs-TA) spectroscopy suggests that photogenerated electrons are transferred from the conduction band of F/TiO2 to the Ti3+ surface states and surface F− ions, expediting the separation of electrons and holes. Consequently, with F− doping in TiO2, the photocatalytic H2O2 production yields improved from 277 to 467 μmol·g−1·h−1, with ethanol as a sacrificial reagent. This study provides a new strategy for regulating the d-band center to optimize the adsorption strength between the photocatalyst and oxygen atoms and achieve enhanced photocatalytic H2O2 production performance.

Enhancing the crystallinity of covalent organic frameworks to achieve improved photocatalytic hydrogen peroxide production under ambient conditions

Photocatalytic production of hydrogen peroxide (H2O2) presents a promising strategy for environmental remediation and energy production. However, achieving clean and efficient H2O2 production under ambient conditions without organic sacrificial agents remains challenging. Enhancing the low crystallinity of covalent organic frameworks (COFs) can promote the separation and transmission of photo-generated carriers, thereby boosting their photocatalytic performance. Herein, we introduce a novel synthetic approach by substituting traditional acetic acid catalysts with organic base catalysts to enhance the crystallinity of β-ketoenamine-linked COF, TpBD-COF. Compared to TpBD-COF-A synthesized using acetic acid catalysts, TpBD-COF-B, synthesized with organic base catalysts, exhibited advancements including increased absorption intensity in the visible spectrum, reduced photoluminescence intensity, enhanced photo-generated carrier separation performance, and a 2.1-fold increase in photocatalytic H2O2 production. Under visible light irradiation, TpBD-COF-B achieved a photocatalytic H2O2 production rate of 533 µmol h−1 g−1 using only air and water, without the need for organic sacrificial agents. Furthermore, TpBD-COF-B also exhibited good performance in long-term catalytic production experiments, tests with actual water bodies, and cyclic usage experiments. This study offers a strategy for enhancing the crystallinity of COFs to improve their photocatalytic activity, with promising applications in clean energy production and environmental remediation.

Pyridine‐Based Covalent Organic Frameworks with Pyridyl‐Imine Structures for Boosting Photocatalytic H2O2 Production via One‐Step 2e− Oxygen Reduction

AbstractBipyridine‐based covalent organic frameworks (COFs) have emerged as promising contenders for the photocatalytic generation of hydrogen peroxide (H2O2). However, the presence of imine nitrogen alters the mode of H2O2 generation from an efficient one‐step two‐electron (2e−) route to a two‐step 2e− oxygen reduction pathway. In this work, we introduce 3,3′‐bipyridine units into imine‐based COF skeletons, creating a pyridyl‐imine structure with two adjacent nitrogen atoms between the pyridine ring and imine linkage. This unique bipyridine‐like architecture can effectively suppress the two‐step 2e− ORR process at the single imine‐nitrogen site, facilitating a more efficient one‐step 2e− pathway. Consequently, the optimized pyridyl‐imine COF (PyIm‐COF) exhibits a remarkable H2O2 production rate of up to 5850 μmol h−1 g−1, nearly double that of pristine bipyridine COFs. This work provides valuable insight into the rational design of functionalized COFs for enhanced H2O2 production in photocatalysis.

Pyridine-Based Covalent Organic Frameworks with Pyridyl-Imine Structures for Boosting Photocatalytic H2O2 Production via One-Step 2e- Oxygen Reduction.

Bipyridine-based covalent organic frameworks (COFs) have emerged as promising contenders for the photocatalytic generation of hydrogen peroxide (H2O2). However, the presence of imine nitrogen alters the mode of H2O2 generation from an efficient one-step two-electron (2e-) route to a two-step 2e- oxygen reduction pathway. In this work, we introduce 3,3'-bipyridine units into imine-based COF skeletons, creating a pyridyl-imine structure with two adjacent nitrogen atoms between the pyridine ring and imine linkage. This unique bipyridine-like architecture can effectively suppress the two-step 2e- ORR process at the single imine-nitrogen site, facilitating a more efficient one-step 2e- pathway. Consequently, the optimized pyridyl-imine COF (PyIm-COF) exhibits a remarkable H2O2 production rate of up to 5850 μmol h-1 g-1, nearly double that of pristine bipyridine COFs. This work provides valuable insight into the rational design of functionalized COFs for enhanced H2O2 production in photocatalysis.

Efficient Electrosynthesis of Hydrogen Peroxide Using Oxygen-Doped Porous Carbon Catalysts at Industrial Current Densities.

Metal-free carbon catalysts (MFCCs) are one of the commonly used catalysts for electrocatalytic two-electron oxygen reduction (2e- ORR) synthesis of hydrogen peroxide (H2O2). Oxygen doping is an effective means to improve the performance of MFCCs, but the performance of oxygen-doped carbon catalysts is still not high enough, and the contribution of different oxygen functional groups (OFGs) to the catalytic performance is still inconclusive. In this paper, carbon-based catalysts with different oxygen contents and ratios of OFGs were prepared, and the high 2e- ORR activity of COOH + C-OH was demonstrated by combining the results of experiments and theoretical calculations. The prepared oxygen-doped carbon-based catalyst C-0.1M80 achieved an onset potential of 0.795 V (vs RHE), a selectivity of up to 98.2% (0.6 V vs RHE), and a H2O2 oxidation current of 1.33 mA cm-2 (0.5 V vs RHE) in a rotating ring-disk electrode test (0.1 M KOH solution), which was an outstanding performance in MFCCs. In a solid electrolyte flow cell, C-0.1M80 achieved a Faraday efficiency of 97.5% at 200 mA cm-2 with a corresponding H2O2 production rate of 123.7 mg cm-2 h-1. In addition, a flow cell stability test was performed at an industrial current density (100 mA cm-2) with an astounding 200 h of uninterrupted operation, also achieving an outstanding average Faradaic efficiency (95.8%).