Bimetallic Sites Research Articles

Cu−based bimetallic sites' p-d orbital hybridization promotes CO asymmetric coupling conversion to C2 products

Hampered by sluggish C−C coupling kinetics, the low selectivity and efficiency have limited industrial applications of CO2 reduction into valuable multi-carbon products. A direct coupling of CO molecules or their coupling after hydrogenation, followed by the final synthesis of C2 products, can help to overcome these limitations potentially. In this study, a detailed high-throughput screening of bimetallic site catalysts comprising copper (Cu) and 28 other metal (M) atoms was conducted. The metal atoms Cu and M were anchored on a carbon nanotube (CNT) with six nitrogen (N6) defects (CuMN6@CNT), which possesses effective dual active sites for C−C coupling. The calculated results demonstrate that the CuGaN6@CNT catalyst exhibited favorable selectivity, with low theoretical overpotentials of −0.23 and −0.34 eV for ethanol and ethylene, respectively, surpassing most reported catalysts. The synergistic effect of Ga and Cu sites, along with their p-d states hybridization, results in an enhancement of Cu's d state dispersion and energy barriers reduction for C−C coupling. Additionally, the strain effect of the substrate CNT exhibits a direct correlation with the catalytic performance of CuGaN6@CNT by adjusting the d-band center of the Cu site and p-band center of the Ga site. These findings provide a novel insights into the electrocatalytic reduction of CO into valuable C2 products using bimetallic single atom catalyst, offering significant guidance for future research endeavors in this field.

DBD plasma assisted synthesis of Ce-MIL-88B(Fe) with electron-rich CUSs and mixed-valent bimetallic sites for enhanced photo-Fenton performance

Iron-based metal-organic frameworks (Fe-MOFs) are regarded as a kind of prospective catalysts for photo-Fenton process. However, high cost, rate-limiting Fe(III)/Fe(II) circulation and limited metal sites greatly restricted the application of Fe-MOFs in photo-Fenton system. Ce-MIL-88B(Fe) was synthesized with mixed-valent bimetallic sites and tunable coordinated unsaturated metal sites (CUSs) using dielectric barrier discharge (DBD) plasma with waste PET. The incorporation of Ce altered the structure and the electron aggregation, as well as induced structural defects. Ce substitution in Fe-MOFs induced the regulation of the ratio of Fe ions and formation of electron-rich CUSs, which were beneficial for the rapid adsorption and activation of H2O2, thus enhancing the photo-Fenton performance. The effect of reaction conditions on TC degradation was investigated by response surface methodology (RSM) combined with Box-Behnken design (BBD). This study demonstrates a new perspective on the construction of bimetallic MOFs for the photo-Fenton system.

Bimetallic NiCo@C with a Hollow Sea Urchin Structure Enables Li-S Batteries to Hasten the Reaction Kinetics and Effectively Inhibit the Shuttling of Polysulfides.

The "shuttle effect" and several issues related to it are seen as "obstacles" to the study and development of lithium-sulfur batteries (LSBs). This work aims at finding how to fully expose bimetallic sites and quicken the battery reaction kinetics. Here, a bimetallic NiCo-MOF and its derivative NiCo@C with a hollow sea urchin structure are produced. The obtained NiCo@C possesses a micromesoporous structure and fully disclosed bimetallic active sites because of its distinctive structure. The experimental findings demonstrate that fully exposed bimetallic active sites take on chemical adsorbents and collaborate with micromesopores as physical constraints to effectively suppress the "shuttle effect". Furthermore, the hollow sea urchin structure of NiCo@C enables a highly conductive grid, which provides channels to facilitate the movement of solvated Li+. Thanks to these advantages, the NiCo@C-based sulfur cathode offers a high initial discharge specific capacity of 924.41 mAh g-1 at 0.1 C and sustains 390.35 mAh g-1 discharge specific capacity after 100 cycles. The quick transfer of solvated lithium ions (DLi+ = 1.81 × 10-8 cm2 s-1) enables the battery to still contribute a discharge specific capacity of 367.54 mAh g-1 at 1 C. This work provides a new understanding for the structural design of positive electrodes in LSBs.

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.

Photothermal Synergistic Effect Induces Bimetallic Cooperation to Modulate Product Selectivity of CO2 Reduction on Different CeO2 Crystal Facets

AbstractProduct selectivity of solar‐driven CO2 reduction and H2O oxidation reactions has been successfully controlled by tuning the spatial distance between Pt/Au bimetallic active sites on different crystal facets of CeO2 catalysts. The replacement depth of Ce atoms by monatomic Pt determines the distance between bimetallic sites, while Au clusters are deposited on the surface. This space configuration creates a favourable microenvironment for the migration of active hydrogen species (*H). The *H is generated via the activation of H2O on monatomic Pt sites and migrate towards Au clusters with a strong capacity for CO2 adsorption. Under concentrated solar irradiation, selectivity of the (100) facet towards CO is 100 %, and the selectivity of the (110) and (111) facets towards CH4 is 33.5 % and 97.6 %, respectively. Notably, the CH4 yield on the (111) facet is as high as 369.4 μmol/g/h, and the solar‐to‐chemical energy efficiency of 0.23 % is 33.8 times higher than that under non‐concentrated solar irradiation. The impacts of high‐density flux photon and thermal effects on carriers and *H migration at the microscale are comprehensively discussed. This study provides a new avenue for tuning the spatial distance between active sites to achieve optimal product selectivity.

Photothermal Synergistic Effect Induces Bimetallic Cooperation to Modulate Product Selectivity of CO2 Reduction on Different CeO2 Crystal Facets.

Product selectivity of solar-driven CO2 reduction and H2O oxidation reactions has been successfully controlled by tuning the spatial distance between Pt/Au bimetallic active sites on different crystal facets of CeO2 catalysts. The replacement depth of Ce atoms by monatomic Pt determines the distance between bimetallic sites, while Au clusters are deposited on the surface. This space configuration creates a favourable microenvironment for the migration of active hydrogen species (*H). The *H is generated via the activation of H2O on monatomic Pt sites and migrate towards Au clusters with a strong capacity for CO2 adsorption. Under concentrated solar irradiation, selectivity of the (100) facet towards CO is 100 %, and the selectivity of the (110) and (111) facets towards CH4 is 33.5 % and 97.6 %, respectively. Notably, the CH4 yield on the (111) facet is as high as 369.4 μmol/g/h, and the solar-to-chemical energy efficiency of 0.23 % is 33.8 times higher than that under non-concentrated solar irradiation. The impacts of high-density flux photon and thermal effects on carriers and *H migration at the microscale are comprehensively discussed. This study provides a new avenue for tuning the spatial distance between active sites to achieve optimal product selectivity.

Creating CoRu Dual Active Sites Codecorated Stable Porous Ceria Support for Enhanced Li-CO2 Batteries Cathodes.

Lithium-carbon dioxide (Li-CO2) battery represents a high-energy density energy storage with excellent real-time CO2 enrichment and conversion, but its practical utilization is hampered by the development of an excellent catalytic cathode. Here, the synergistic catalytic strategy of designing CoRu bimetallic active sites achieves the electrocatalytic conversion of CO2 and the efficient decomposition of the discharge products, which in turn realizes the smooth operation of the Li-CO2 battery. Moreover, obtained support based on metal-organic frameworks precursors facilitates the convenient diffusion and adsorption of CO2, resulting in higher reaction concentration and lower mass transfer resistance. Meanwhile, the optimization of the interfacial electronic structure and the effective transfer of electrons are achieved by virtue of the strong interaction of CoRu at the support interface. As a result, the Li-CO2 cell assembled based on bimetallic CoRu active sites achieved a discharge capacity of 19,111mAhg-1 and a steady-state discharge voltage of 2.58V as well as a cycle life of >175 cycles at a rate of 100mAg-1. Further experiments combined with density-functional theory calculations achieve a deeply view of the connection between cathode and electrochemical performance and pave a way for the subsequent development of advanced Li-CO2 catalytic cathodes.

Asymmetric bridge structure based on NiFe bimetallic sites for optimizing nitrate reduction reaction

Asymmetric bridge structure based on NiFe bimetallic sites for optimizing nitrate reduction reaction

Architecting double-shelled hollow carbon nanocages embedded bimetallic sites as bifunctional oxygen electrocatalyst for zinc-air batteries

Rational design of complex hollow nanostructures offers a great opportunity to construct various functional nanostructures. A novel in situ disassembly-polymerization-pyrolysis approach was developed to synthesize atomically dispersed Fe single atoms (Fe SAs) and tiny Co nanoparticles (Co NPs) binary sites embedded in double-shelled hollow carbon nanocages (Co NPs/Fe SAs DSCNs) without removing excess templates. The Co NPs/Fe SAs DSCNs displayed excellent bifunctional activity, boosting the realistic rechargeable zinc-air batteries with high efficiency, long-term durability, and reversibility, which is comparable to noble metal catalysts (Pt/C and RuO2). The enhanced catalytic activity should be attributed to as well as the strong interactions between Fe SAs and Co NPs with the nitrogen-doped carbon matrix, the exposure of more active sites, and the high-flux mass transportation. In addition, the confinement effect between the double C-N shells prevented the aggregation and corrosion of metal atoms, thus improving the durability of the Co NPs/Fe SAs DSCNs, further highlighting the structural advantages of carbon nanoreactor. This work provides guidance for further rational design and preparation of complex hollow structure materials with advanced bifunctional air cathodes.

Recognizing the relevance of non-radical peroxymonosulfate activation by co-doped Fe metal-organic framework for the high-efficient degradation of acetaminophen: Role of singlet oxygen and the enhancement of redox cycle

A bimetallic MOF derivative consisting of Fe and Co (Fe/Co2-MOF) by Co-doping MIL-101(Fe) was successfully synthesized for peroxymonosulfate (PMS) activation in acetaminophen (N-Acetyl-Para-Amino-Phenol, APAP) degradation. The presence of Co significantly accelerated the transfer of electrons due to the synergistic effect between Fe and Co bimetallic sites. Specifically, the reaction rate constant of APAP in the Fe/Co2-MOF + PMS system was three orders of magnitude higher than that of MIL-101(Fe) alone and 90 times higher than that of the MIL-101(Fe) + PMS system, respectively. At room temperature, 100 % of the APAP was degraded in 15 min with a Fe/Co2-MOF concentration of 0.05 g/L and a PMS concentration of 0.8 mmol/L across a wide pH range from 3 to 9. High-valence metal species (CoIV and FeIV) and electron transfer-dominated nonradical processes were responsible for the APAP degradation. Although singlet oxygen (1O2) was identified as the main active species in our study, the relative contribution of 1O2 was negligible. The catalytic performance was particularly notable in the practical implementation of hospital sewage treatment. However, it is still urgent to seek ways to relieve cobalt leaching of Fe/Co2-MOF. This strategy of Co-doping provides a clear illustration of modulating MIL-101(Fe) ultimately maximize their catalytic efficiency in PMS activation for water purification.

Bimetallic MIL-68(InFe) MOF nanorods for biomimetic photocatalytic N2 fixation

This work develops a series of bimetallic MIL-68(InFe) MOF nanorods (NM(In1-xFex)) mimicking the nitrogenase for biomimetic photocatalytic N2 fixation. The partial substitution of In3+ with Fe3+ leads to the electron redistribution from In3+ to Fe3+, generating electron-poor In3+ (In(3+δ)+) sites and electron-rich Fe3+ (Fe(3–δ)+) sites as an electron acceptor–donor combination to promote the N2 activation by a π back-donation mechanism. The smaller size of the nanorods further provides more accessible active sites than the bulk counterpart. In cooperation with the H+ released from the H2O, the activated N2 molecules were reduced by photogenerated electrons to give NH3. The optimal sample NM(In0.90Fe0.10) exhibited the highest NH4+ production rate of 30.8 µmol·h−1·g−1 without any sacrificial agent, attributed to the presence of abundant In/Fe bimetallic sites for N2 activation and enhanced charge mobility. This work provides new insights into rational design for artificial N2 fixation systems by mimicking natural nitrogenase.

0D–2D multifunctional bimetallic MOF derivative-MXene heterojunction for high areal capacity lithium-sulfur batteries

Lithium-sulfur (Li-S) batteries have attracted much attention due to their high specific capacity. However, at high loads and rates, the polysulfides conversion rate and ion transport of batteries are slow, limiting their commercialization. This work reports zero-dimensional (0D) bimetallic MOF derivatives grown in situ on two-dimensional (2D) MXene by electrostatic adsorption (FeCo@Ti3C2). The 0D bimetallic structure effectively avoids the stacking of MXene while providing a dual catalytic site for polysulfides. The 2D structure of MXene also provides a large number of pathways for the rapid diffusion of lithium ions. This 0D–2D heterostructured heterogeneous catalyst with bimetallic synergistic active sites efficiently immobilizes and catalyzes polysulfides, providing a fast charge transfer pathway for the electrochemical reaction of lithium polysulfides. The Li-S battery with this multifunctional 0D–2D heterojunction structure catalyst has outstanding high rate capacity (703 mAh g−1 at 4 C at room temperature and 555 mAh g−1 at 2 C at 0 °C), fascinating capacity at high load (5.5 mAh cm−2 after 100 cycles at a high sulfur content of 8.2 mg cm−2). The study provides new ideas for the commercialization of high-efficiency Li-S batteries.

Constructing Cu-Mn bimetallic synergistic sites in 2D metal-organic framework nanosheets to induce polarized charge distribution: Electronic structure transformation and evaluation of Fenton-like performance

Heterogeneous Fenton-like process based on H2O2 was an efficient method for the abatement of micropollutants in water. However, the mass transport resistance caused by the limited access between catalytic sites and target chemicals still restrict the decontamination efficiencies. Metal-organic frameworks (MOFs) with uniformed pores and anbundant metal sites shows great potentail in environmental remediation, Here, a novel two-dimensional nanosheet consisting of Cu and Mn bimetallic-oxygen clusters (CuMn-BDC, BDC refers to terephthalic acid organic ligand) was rationally designed and characterized. The introduction of second metal Mn changed the surface electronic distribution and accelerated the electron transfer of pristine Cu-based nanosheet, leading to improved catalytical acticities and removal effeciencies (kSA) for Sulfamethoxazole (SMX). The catalytic activity of CuMn-BDC obtained (5.76 × 10–4) was 3.95 times higher than that of Cu-BDC (1.46 × 10–4), demonstrating that the CuMn-BDC showed higher reaction rates than that of Cu-BDC when same amount of H2O2 was added. The interfacial micro-electric fields in bimetallic MOFs increased the interaction of organic pollutants and transfer the electron to activate H2O2. Several quenching experiments, electron paramagnetic resonance spectra and theoretical calculations were performed to study the reaction mechanism systematically. Further the powder was fabricated into membrane with higher water stablities. This study shed light on develop efficient 2D-MOFs catalyst for the abatement of micropollutants in water.

Boosting hydrogenation properties of supported Cu-based catalysts by replacing Cu0 active sites

Balancing the Cu+/Cu0 ratio is a common strategy to improve catalytic activity of Cu-based catalysts but is still constrained by low atomic utilization and the inherent nature of charge distribution. Herein, we reported a strategy of replacing the Cu0 active sites in Cu-based catalysts by constructing bimetallic sites on ceria, which consist of spatially separated trace amounts of palladium metal and plate-shaped Cu+ clusters with one-atom layers. The catalytic activity of the prepared Cu100Pd1/CeO2-FA catalyst (using formic acid) was 4 times that of conventional Cu100Pd1/CeO2-H catalyst in selective hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan, even outperforming some existing noble metal catalysts. Multiple characterizations and theoretical calculations demonstrated that the Pd atom is the heterolytic activation site for H2 molecules while plate-shaped Cu+ metal clusters act as effective hydrogenation places. This directional control involving both spatial relationship and electronic structure of the active site provides a new strategy for designing hydrogenated catalysts.

Co doping induces CoxP-Ni2P bimetallic site and acid synergistic effect to achieve efficient hydrodeoxidation

The development of highly efficient hydrodeoxidation (HDO) catalyst is the key to upgrade the quality of bio-oil. CoxP-Ni2P/SiO2-y catalysts (y is the initial P/(Ni+Co) molar ratio) comprised of CoxP-Ni2P bimetallic sites and acidic site were prepared by doping Co into Ni2P active phase using mesoporous SiO2 as the support. The structure and chemical properties of the catalyst were characterized by XRD, BET, XPS, H2-TPR, NH3-TPD, Py-FTIR and TEM methods. The effects of Co doping and P/M molar ratio on the HDO performance of Ni2P/SiO2 catalyst were investigated taking m-cresol as the model compound. The results show that Co doping not only creates new CoxP active sites, but also optimizes the electronic structure of Ni2P, thus improving the HDO activity of the catalyst. Among the CoxP-Ni2P/SiO2-y catalysts, CoxP-Ni2P/SiO2-0.5 with P/M molar ratio of 0.5 exhibits the best catalytic performance, with the m-cresol conversion of 98.7% and selectivity to the deoxidized product methylcyclohexane (MCH) of 95.6% at 275 °C, 2 MPa and 1 h. The HDO of m-cresol over the CoxP-Ni2P/SiO2-y catalyst mainly proceeded through hydrogenation-deoxygenation (HYD) pathway.

Bimetallic site substitution of NiCoP nanoneedles as bifunctional electrocatalyst for boosted water splitting

Bimetallic site substitution of NiCoP nanoneedles as bifunctional electrocatalyst for boosted water splitting

Layered Porous Ring-Like Carbon Network Protected FeNi Metal Atomic Pairs for Bifunctional Oxygen Electrocatalysis and Rechargeable Zn-Air Batteries.

Bimetallic atom catalysts exhibit ultra-high oxygen electrocatalytic activity by harnessing mutual promotion and synergistic effects between adjacent metal active centers, surpassing the performance of single metal atomic catalysts. Herein, FeNi atom pairs protected by hierarchical porous annular carbon grids (P-FeNi-NPC) are introduced using a mediator-assisted MOFs-derived strategy. The introduction of the multi-block copolymer P123 ensures the uniform confinement and dispersion of metal ions, followed by thermal decomposition to form a "planetary-ring-like" carbon framework that anchors the bimetallic atomic pairs in the active region. The homogeneous distribution of adjacent Fe-N4 and Ni-N4 active sites significantly enhances catalytic activity and stability. Leveraging unique electronic and geometric structures, the resulting P-FeNi-NPC catalyst demonstrates exceptional ORR and OER activities with an ΔE value of 0.705 (E1/2 = 0.845V, Ej = 10 = 1.55V). Theoretical calculations unveil that FeNi bimetallic sites loaded on nitrogen-doped carbon frameworks with specific curvature effectively modulate the energy of d-band centers, thus balancing the free energy of oxygen-containing intermediates. This study presents a novel and versatile approach for synthesizing advanced bifunctional catalysts, poised to drive the future development of Zn-air batteries.

Unveiling the mechanistic synergy in Mn-doped NiO catalysts with atomic-burry structure: Enhanced CO oxidation via Ni-OH and Mn bifunctionality

The development of non-noble metal catalysts for low-temperature CO oxidation is a pivotal subject in various disciplines. In this study, an optimized Mn-doped NiO catalyst (Mn-NiO-0.5), prepared via aerosol pyrolysis with an equal molar ratio of Ni to Mn, demonstrates remarkable performance. It achieves an 82 % CO conversion at -20 °C and a 100 % conversion between 10 °C and 800 °C. The catalyst’s turnover frequency (TOF) for CO oxidation significantly surpasses that of previously reported noble-metal-based catalysts, underscoring its superior efficiency. Dynamic analyses suggest that the enhanced catalytic activity is a result of the unique atom burr structure, which presents an extensive surface area replete with abundant active sites. This structural feature is instrumental in maximizing the catalyst’s interaction with CO molecules. Experimental findings, corroborated by density functional theory (DFT) calculations, elucidate the mechanism of CO oxidation on the Mn-NiO-0.5 catalyst. The process is facilitated by the synergistic action of bimetallic sites, where the Ni–OH site acts as the primary adsorption point for CO. Subsequently, the CO is oxidized to bicarbonate through the interaction with the oxygen (O or O2) at adjacent Mn sites. This pioneering study introduces a paradigm-shifting insight: the effectiveness of non-noble metal oxide catalysts can now compete with, and in some cases, outperform their noble metal counterparts. This breakthrough is set to transform the industry, presenting a compelling alternative to conventional noble metal catalysts and propelling the evolution of state-of-the-art environmental conservation technologies.

Improvement of heterogeneous electro-Fenton oxidation of dimethyl phthalate by embedding Fe/Co bimetallic active sites into waste wine lees biochar

Phthalates (PAEs) are frequently detected in the water environment and pose a severe threat to the ecosystem and human health. Electro-Fenton technology is regarded as an effective approach to degrade PAEs; however, the preparation of inexpensive and efficient cathode materials has restricted its further application. In this study, Fe/Co bimetallic sites were incorporated into solid waste wine lees to synthesize highly active heterogeneous catalyst, and dimethyl phthalate (DMP) was chosen as the target pollutant to investigate the activity of the catalyst. Both the degradation of DMP and the removal of total organic carbon (TOC), the performance of Fe/Co co-modified biochar (FeCo@NOPC) is superior to that of Fe (Co) alone (Fe@NOPC/Co@NOPC) and modified biochar (NOPC). Under neutral conditions. Within 5 h, the DMP removal rate reached 89 % and TOC was reduced by approximately 40 %. The mechanism study reveals that the degradation of DMP is mainly attributed to the OH generated by the cathode, and the anodic oxidation and cathode adsorption only play minor roles. Finally, the degradation path of DMP was analyzed by LC-MS technique. This study offers a novel way to utilize solid waste and reduce the cost of heterogeneous electro-Fenton system.