H2O2 Yield Research Articles

Electrocatalysts for the Formation of Hydrogen Peroxide by Oxygen Reduction Reaction.

Hydrogen peroxide (H2O2) is a widely used strong oxidant, and its traditional preparation methods, anthraquinone method, and direct synthesis method, have many drawbacks. The method of producing H2O2 by two-electron oxygen reduction reaction (2e- ORR) is considered an alternative strategy for the traditional anthraquinone method due to its high efficiency, energy saving, and environmental friendliness, but it remains a big challenge. In this review, we have described the mechanism of ORR and the principle of electrocatalytic performance testing, and have summarized the standard performance evaluation techniques for electrocatalysts to produce H2O2. Secondly, according to the theoretical calculation and experimental results, several kinds of efficient electrocatalysts are introduced. It is concluded that noble metal-based materials, carbon-based materials, non-noble metal composites, and single-atom catalysts are the preferred catalyst materials for the preparation of H2O2 by 2e- ORR. Finally, the advantages and novelty of 2e- ORR compared with traditional methods for H2O2 production, as well as the advantages and disadvantages of the above-mentioned high-efficiency catalysts, are summarized. The application prospect and development direction of high-efficiency catalysts for H2O2 production by 2e- ORR has been prospected, which is of great significance for promoting the electrochemical yield of H2O2 and developing green chemical production.

Surface‐Interface Engineering of Electrocatalysts for Two‐Electron Water Oxidation Reaction to Produce H2O2

AbstractElectrochemical two‐electron water oxidation reaction (2e− WOR) driven by renewable energy offers an attractive route to produce H2O2, while the corresponding electrocatalyst still requires further improvement for the activity, selectivity, and the resulting H2O2 yield. Surface‐interface engineering of electrocatalysts has great potential to advance 2e− WOR performance. This review provides a succinct yet comprehensive insight into the functional mechanisms of surface‐interfacial properties affecting 2e− WOR performance on electrocatalyst. The Gibbs free energy theoretical framework related to surface electronic structure and interfacial reactive kinetics mechanism related to electrolyte, electrode–electrolyte interface structure, and interfacial microenvironment properties are firstly discussed. Afterward, various surface‐interface engineering strategies toward high performance electrocatalysts including the regulation of surface electronic structure, the electrode–electrolyte interface structure, and the interfacial microenvironment have been overviewed. Rational manipulations of the above surface‐interfacial engineering strategies are critical to design highly efficient 2e− WOR electrocatalysts, leading to the development of the green H2O2 production.

Evaluation of H2O2, H2, and bubble temperature in the sonolysis of water and aqueous t-butanol solution under Ar: Effects of solution temperatures and inorganic additives of NaCl and KI

The yields of H2O2 and H2 formed in the sonolysis of aqueous solution under noble gas are representative indexes for understanding the chemical effects of ultrasonic cavitation bubbles. In this study, the yields of H2O2 and H2 formed under Ar were evaluated as a function of the concentration of NaCl or KI. When these yields were analyzed by using a normalization technique, it was confirmed that the yields of H2 were more clearly related to Ar solubility than those of H2O2, suggesting that H2 is a more real probe to understand the chemical effects of cavitation bubbles in water. The effects of NaCl on sonochemical formation of oxidants were also compared with those of KI. When aqueous t-butanol solution was sonicated, the yields of H2 and the maximum temperature attained in a collapsing bubble (bubble temperature) decreased with increasing solution temperature and salt concentration, suggesting that these parameters affected the quantity related to the number (and/or size) of active bubbles as well as the quality related to the bubble temperatures.

Fabrication of g-C3N4 wrapped CAU-17 for efficient photocatalytic H2O2 production

Recently, photocatalytic production of H2O2 by semiconductors emerges as a green and potential method for green and sustainable H2O2 synthesis. In this work, a g-C3N4/CAU-17 composite with heterojunction structure was fabricated. There is a tight interface contact between g-C3N4 and CAU-17. And the g-C3N4 nanosheets was uniformly wrapped on CAU-17 surface. In the hybrid catalyst, CAU-17 provides a high surface area for g-C3N4 dispersion and the integration of g-C3N4 boosts the visible light response. Results showed that the H2O2 yield is 419.0 μmol.L-1.h-1 over g-C3N4/CAU-17 sample, which is 1.59 and 7.83 fold enhancements to bare g-C3N4 and CAU-17 counterparts. This work sheds light on the design of CAU-17-based composite photocatalysts and provides insights into H2O2 synthesis.

CuO/Cu(OH)2@g-C3N4 derived from CuBTC/g-C3N4 for two channel photocatalytic hydrogen peroxide production

Photocatalytic production of H2O2 is indeed a safe, sustainable and cost-effective technology, offering an environmentally friendly solution to the energy crisis through solar photocatalysis. However, it still faces challenges such as reliance on organic electron donors and pure O2, as well as inefficiencies in hole utilization. To overcome these limitations, a dual-channel photocatalytic system has been developed. In this study, we showcase the efficiency of the CuO/Cu(OH)2@g-C3N4 composite, derived from CuBTC/g-C3N4 via NaOH treatment, as a high-performance dual-channel photocatalyst for H2O2 production. Under visible light (λ ≥ 420 nm), this composite achieves a H2O2 yield of 1354 μmol/L in 120 min without any sacrificial agent, outperforming g-C3N4 by 8.4 times, CuO by 13.6 times and CuO@g-C3N4 by 1.9 times. Quenching experiments and electron paramagnetic resonance spectra confirmed that HO• and O2•− are intermediate products in the photocatalytic process, following a two-step single-electron reaction pathway. The superior activity of CuO/Cu(OH)2@g-C3N4 in H2O2 generation can be attributed to the synergistic effects of OH bonds on the CuO@g-C3N4 Z-type heterojunction and Cu(OH)2. This research presents a straightforward and promising approach for developing highly efficient photocatalysts for energy conversion.

Perfect Is Perfect: Nickel Prussian Blue Analogue as A High‐Efficiency Electrocatalyst for Hydrogen Peroxide Production

AbstractPrussian blue analogues (PBA) are a large family of functional materials with diverse applications such as in electrochemical fields. However, their use in the emerging two‐electron oxygen reduction reaction for clean production of hydrogen peroxide (H2O2) is lagging. Herein, a general solvent exchange induced reconstruction strategy is demonstrated, through which an abnormal NiNi‐PBA superstructure is synthesized as a high‐performance electrocatalyst for H2O2 generation. The resultant NiNi‐PBA superstructure has a stoichiometric composition with saturated lattice water, and a leaf‐like morphology composed of interconnected small‐size nanosheets with identical orientation and predominate {210} side surface exposure. Our studies show that the Ni−N centers on {210} facets are the active sites, and the saturated lattice H2O favors a six‐coordinated environment that results in high selectivity. The “perfect” structure including stoichiometric composition and ideal facet exposure leads to a high selectivity of ~100 % and H2O2 yield of 5.7 mol g−1 h−1, superior to the reported MOF‐based electrocatalysts and most other electrocatalysts.

Phase Reconstruction‐Directed Synthesis of Oxalate‐Functionalized Nickel Hydroxide Electrocatalyst for High‐Yield H2O2 Generation at Industrial Currents

AbstractThe electrochemical oxygen reduction reaction (2e− ORR) offers a promising approach for H2O2 production, yet developing highly active, selective, and stable electrocatalysts remains a challenge. In this work, a phase reconstruction strategy is presented to synthesize an oxalate‐adsorbed nickel hydroxide electrocatalyst (Ni(OH)2‐C2O4) through the self‐dissociation of nickel oxalate in an alkaline medium, leading to a notable enhancement in H2O2 yield at elevated current densities. Remarkably, Ni(OH)2‐C2O4 exhibits a 2e− selectivity exceeding 93% across a broad voltage range (0.0 to 0.5 V vs RHE) in 0.1 M KOH, outperforming pristine Ni(OH)2. When deployed as a gas diffusion electrode in a flow cell, the Ni(OH)2‐C2O4 catalyst demonstrates stable operation for 50 h at 200 mA cm−2, with a Faradaic efficiency surpassing 90% and a peak H2O2 yield of 6.2 mol g−1cat h−1. Comprehensive advanced characterizations, including in situ Raman spectroscopy, transient photovoltage spectra, and transient potential scanning spectra, coupled with post‐ORR analyses, reveal that surface‐adsorbed oxalate groups on Ni(OH)2 enhance the interfacial reaction kinetics between active Ni sites and reactants by inducing a charge trapping effect and forming a hydrogen‐bonded network, facilitating robust and high‐yield H2O2 production.

Construction of pyrrolo[3,2-b]pyrrolyl-linked covalent organic polymers to promote continuous overall H2O2 production

Sacrificial agent-free, solar-driven photocatalytic oxygen reduction holds promise for hydrogen peroxide production. However, the rapid recombination of electron–hole pairs in catalysts and the slow diffusion rate of oxygen on the catalyst surfaces significantly hinder the efficiency of hydrogen peroxide production. To address these issues, we developed a novel class of pyrrolo[3,2-b]pyrrolyl-linked covalent organic polymers (COPs) combined with microreactor technology to enhance hydrogen peroxide synthesis. These structurally well-defined polymers feature photoactive pyrrolo[3,2-b]pyrrolyl units were assembled from aldehyde, aniline, and 2,3-butanedione through a one-pot three-component reaction. Integrating pyrrolo[3,2-b]pyrrolyl moieties into the COPs creates donor–acceptor structures that facilitate the separation of photogenerated electrons and holes. Among them, COP-2 achieved the highest H2O2 yield of 5446 μmol g−1 h−1. Furthermore, we designed a coiled tube photomicroreactor to improve mass transfer efficiency in the gas–liquid–solid triphase system, boosting the H2O2 yield to 20285 μmol g−1h−1 without the need for a sacrificial agent. This study offers new insights into integrating polymer photocatalysts with microflow technology, underscoring the potential for future green and continuous H2O2 production.

Undervalued role of metal-carbon junction in selective generation of H2O2: An example of the zinc-carbon junction edge providing asymmetric active sites for efficient oxygen reduction

The spontaneous oxygen reduction is a potential technology for in-situ H2O2 production, which gets rid of the dependence on electricity and solar energy. Previous some metal–carbon compounds reported are feasible to trigger oxygen reduction. These reports always claim the high H2O2 generation ability of metal–carbon composites, while rarely discuss the contribution of carbon and the carbon–metal junction to the oxygen reduction process. Inspired by the dual active sites, we infer that the role of interfacial carbon in metal–carbon composites is underestimated. By a heat treatment of the co-precipitate of zinc and glucose, the Zn-C junction is constructed in Zn-gc to achieve a spontaneous selective reduction of O2 to H2O2. The Zn-C interface edge is active site, where an asymmetric activation is achieved by bonding two O atoms from O2 to C and Zn, respectively. The Zn traction to one of the O atoms is mainly in xy plane, while the C traction to the other O atom is parallel to z-axis. The yield of H2O2 produced per gram of Zn increases from 27.89 mg to 122.21 mg, an improvement of 4.38 times. And the inertness of Zn and its oxygen-containing compounds towards H2O2 enables Zn-gc/O2 system to stabilize H2O2 over a long period of time. This work reveals the crucial role of neglected junction interfaces in oxygen reduction reactions in metal–carbon composites.

Modulating Yeager Adsorption Configuration of O2 Through Cd Doping in Zn3In2S6 for Photosynthesis of H2O2

AbstractThe photocatalytic oxygen reduction reaction (ORR) is a key pathway for producing hydrogen peroxide (H2O2). While most previous studies have focused on the two‐step 2e− ORR process, the one‐step two‐electron ORR route offers thermodynamic and kinetic advantages that can significantly enhance 2e− ORR activity and selectivity. In this study, a photocatalyst design is reported by incorporating cadmium into vacancy‐rich Zn3In2S6 (Cd‐SV/ZIS). This catalyst enables H2O2 production via a one‐step 2e− ORR process without the use of sacrificial agents, achieving a high H2O2 yield of 39.42 µmol g−1 min−1 under UV–vis light irradiation, outperforming most reported ZIS‐based photocatalysts. Theoretical simulations and experimental results demonstrate that Cd doping improves the carrier kinetics of the catalyst, broadens its light absorption range, and promotes the Yeager adsorption configuration of O2, leading to highly active and selective H2O2 generation. This study provides insights into the design of efficient ZIS‐based photocatalysts for H2O2 production.

Fabrication of boron modified bi-functional air diffusion electrode for ciprofloxacin degradation: In-situ H2O2 generation and self-activation

In order to improve H2O2 in-situ generation in electrochemical system, a boron (B) modified air diffusion electrode (B@ADE) was fabricated in the present study. Carbon black (CB) doped by B was deposited on ADE surface as catalytic layer. Performance of B@ADE with different B/C mass ratios has been investigated and 0.3 was identified as the optimal one·H2O2 yield can be achieved 204.85 mg L-1 within 45 min at 0.3-B@ADE, which was 1.51 times for that of ADE. Meanwhile, H2O2 self-activation on B@ADE surface was observed and effects of different operating parameters on •OH formation have been analyzed. XPS analyzation demonstrated that BC2O, BC2O and C=O/O-C=O were related to H2O2 generation. DFT calculation revealed that BCO2 was benefit for O2 adsorption, while BC2O promoted *OOH desorption with lower free energy barriers for H2O2 and •OH generation. Quenching experiments for ciprofloxacin (CIP) demonstrated that •OH, O2•- and 1O2 were co-existed in the system with their contribution quantified. Four possible degradation pathways were proposed through active sites identification by DFT calculation and intermediates detection by HPLC-MS/MS. Bio-toxicity analyzation results showed that the toxicity of most intermediates was lowered than CIP. These results proved that electrochemical oxidation system with B@ADE enhanced in-situ H2O2 generation and self-activation, with great potential for practical application.

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.

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

AbstractElectrochemical 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.

Alkali metal cation adsorption–induced surface polarization in polymeric carbon nitride for enhanced photocatalytic hydrogen peroxide production

Photocatalytic hydrogen peroxide (H2O2) generation on the catalyst surface from oxygen is an electron-demanding process, making the construction of an electron-rich surface highly advantageous. In this study, a localized electric field was observed on the surface of polymeric carbon nitride (g-C3N4) when alkali metal cations were adsorbed onto it. These fields effectively inhibited surface carrier recombination and extended their lifespan, thereby enhancing H2O2 production. As a result, g-C3N4 achieved a superior H2O2 yield of 2.25 mM after 1 h in a 0.25 M K+ solution, which was 2.06 times greater than that (1.09 mM) achieved in a pure solvent. Notably, the increase in photocatalytic efficiency showed a remarkable dependence on ion species. At low concentrations, H2O2 generation efficiency was in the order of Li+ < Na+ < K+ < Rb+ < Cs+. However, after optimizing the ion concentration, the highest H2O2 production was achieved in a solution containing K+ instead of Cs+. Molecular dynamics simulations and temperature-dependent photocatalysis experiments revealed that the synergistic interaction between adsorption energy and adsorption distance was crucial in governing the extent to which alkali metal cation adsorption enhanced g-C3N4 photocatalytic H2O2 production. This study provides theoretical insights for the design of materials for electron-demanding photocatalysis and aids in understanding variations in photocatalytic behavior in natural waters.

Hydroxyl-enriched hydrous tin dioxide-coated BiVO4 with boosted photocatalytic H2O2 production

The rapid decomposition of H2O2 on the surface of inorganic photocatalyst (BiVO4) and insufficient proton supply from water leads to a low photosynthetic yield of H2O2. Herein, hydrous tin dioxide (HSnO) with massive hydroxyl groups was coated on the BiVO4 surface to greatly improve the photocatalytic H2O2 activity via simultaneous realization of providing sufficient protons and inhibiting H2O2 decomposition. After the coating of HSnO, Au nanoparticles as the O2-reduction active sites were selectively deposited on the (010) facet of BiVO4 to synthesize the Au/BiVO4@HSnO photocatalyst. The resulting Au/BiVO4@HSnO photocatalyst exhibits excellent H2O2-production performance, in which the photogenerated H2O2 concentration (210.7 ​μmol ​L−1) is about 4.8 times higher than that of the Au/BiVO4 after 2 ​h light irradiation in pure water. The outstanding photocatalytic performance can be attributed to simultaneous enhancement of H2O2 generation and the suppression of H2O2 decomposition by HSnO coating. Specifically, the HSnO coating with massive hydroxyl groups provides enough protons to promote the catalytic transformation of O2 into H2O2 on Au nanoparticles. More importantly, the HSnO coating not only allows water macular to effectively permeate onto BiVO4 surface for rapid oxidation reaction, but also greatly inhibits the reverse reaction of H2O2 decomposition via decreasing its affinity with BiVO4 surface. This research offers new insights for boosting photocatalytic H2O2 production through surface coating strategy.

Bi3TiNbO9/Bi2S3 Heterojunction for Efficient Photosynthesis of H2O2 in Pure Water

AbstractHeterojunction engineering has been deemed one of the most promising strategies for promoting charge separation and improving solar‐to‐chemicals efficiency. Howbeit, constructing well‐defined nanoheterojunction with superior photocatalytic activity for H2O2 generation and a clear reaction mechanism remains a formidable challenge. Herein, an in situ vulcanization way to synthesize an intriguing 2D/1D Bi3TiNbO9/Bi2S3 heterojunction by growing Bi2S3 nanorods on Bi3TiNbO9 microsheet is used for the first time, where an S‐scheme charge transfer mechanism is formed that facilitates the spatial separation of charge carriers. Moreover, the in situ grown Bi2S3 on Bi3TiNbO9 can optimize the interfacial electronic structure and the reaction energy barriers. As a result, the H2O2 yield rate for Bi3TiNbO9/Bi2S3 can reach 810(2) µmol g−1 h−1 without any sacrificial agents and cocatalysts, ≈6.18 and ≈18.0 times of pristine Bi3TiNbO9 and Bi2S3, respectively. Importantly, the heterojunction unveiled unprecedented stability, remaining ≈95.46(2)% of the initial one after 13 continuous cycles. This work highlights an innovative in situ vulcanization strategy to engineer oxide perovskite/metal sulfide nanocomposite catalysts for artificial photosynthesis of H2O2, opening new opportunities for achieving highly efficient photocatalyst systems.

Properties of palladium-phosphorus catalysts supported on HZSM-5 zeolite in the direct synthesis of hydrogen peroxide

The properties of Pd/HZSM-5 and Pd–nP/HZSM-5 catalysts in direct synthesis and side processes of decomposition and hydrogenation of H2O2 under mild conditions in ethanol and aqueous-ethanol medium in the presence of an acid inhibitor were studied. Using HR-TEM, XRD and ICP MS methods, it was shown that as a result of modification with phosphorus, X-ray amorphous highly dispersed systems are formed, which represent structurally disordered solid solutions of phosphorus in palladium. The main reasons for the promoting effect of phosphorus on the yield of H2O2 are considered. It has been established that, along with phosphorus and acid modifiers, the use of a zeolite support in the H-form favors the inhibition of the side process of H2O2 decomposition.

Doped‐Sn Enhanced the Performance of BiOCl Nanosheet on Electrocatalytic Synthesis of Hydrogen Peroxide

AbstractThe hydrogen peroxide (H2O2) produced through electrochemical two‐electron oxygen reduction reaction (2e− ORR) is a promising green synthesis method and served as potential strategy to replace the energy‐intensive anthraquinone process. Nevertheless, the design of low‐cost and efficient electrocatalysts for 2e− ORR remains a formidable challenge. In this study, Sn‐BiOCl nanosheets electrocatalysts are prepared for expediting the 2e− ORR, achieving a high H2O2 selectivity of 92.9%, and the H2O2 yield of 10628 mg L−1 h−1 (0.1 mg cm−2) in a flow‐cell device. The in situ ATR‐SEIRAS results reveal that Sn‐BiOCl enhances the adsorption and activation of *OOH compared to BiOCl, resulting in higher activity and selectivity for 2e− ORR. Furthermore, this study investigates the potential for on‐site production and application of H2O2 using Sn‐BiOCl, which displays a 95% degradation removal of dyes (RhB, MB, and MO) within 20 min. This work not only have an insight into the critical roles of Bi and Sn atoms in enhancing the catalytic performance but also provides a thought to design efficient catalysts for production H2O2 via electrochemical 2e− ORR.

Novel electron activation of pollutants for driving its energy to boost H2O2 generation and wastewater purification

Dual-photocatalysis for synchronous H2O2 production with contaminant degradation presents a promising approach to addressing the energy crisis and environmental pollutantion that prevails in the indirect conversion of pollutant energy into chemical energy. Herein, a novel activation strategy that leverages visible-light and the n-state sites to harness antibiotic electrons to generate H2O2 in a dual-photocatalysis process is demonstrated. With n-state sites on g-C3N4 (CBCN), ciprofloxacin (CIP) molecules tend to be absorbed on their surface and transfer electrons to the n-state site to lower the surface energy of CIP-CBCN. These electrons stored in the n-state site are then activated by visible-light to reduce molecular oxygen into H2O2. As CIP loses electrons, its degradation is accelerated. Therefore, in this novel electron activation process, the CIP energy is converted into chemical energy, driving the self-degradation of CIP. This results in a remarkable H2O2 yield of 95 μmol L−1 achieved synchronously with 99.9 % CIP removal after 40 min of visible-light irradiation.

A novel MOF-derived Fe/Ce@NPC-600 floating cathode with massive FeII using in photoelectro-Fenton system for efficient degradation of aqueous tetracycline: Fabrication, performance prediction based on machine learning and mechanism

A MOF-derived carbon/metaloxide composite (Fe/Ce@NPC-600) by doping Ce into NH2-MOF-101(Fe) precursor and simple one-step carbonization was fabricated. Fe/Ce@NPC-600 as a floating cathode was innovatively applied to the solar photoelectro-Fenton (SPEF) process to increase the yield of H2O2 and activate it for degradation tetracycline (TC). The characterizations showed that the presence of Ce greatly increased the content of Fe2+ and photoresponse ability in the material. Thanks to the synergistic effect of Fe and Ce, Fe/Ce@NPC-600 cathode could efficiently degrade TC by 98.2% within 30 min, and the removal rate of total organic carbon (TOC) was 68.2%, and the photoelectric synergistic enhancement factor (fPEF) was 1.4. Besides, based on machine learning, a extreme gradient boosting model was established to predict electrode performance. The degradation mechanism and pathway of TC were also proposed. Our results inspired the application of floating cathodes, MOF-derived materials and artificial intelligence for advanced oxidation processes for efficient removal of emerging contaminants.