Main Active Sites Research Articles

Efficient electrocatalytic CO2 reduction to ethylene using cuprous oxide derivatives.

Copper-based materials play a vital role in the electrochemical transformation of CO2 into C2/C2+ compounds. In this study, cross-sectional octahedral Cu2O microcrystals were prepared in situ on carbon paper electrodes via electrochemical deposition. The morphology and integrity of the exposed crystal surface (111) were meticulously controlled by adjusting the deposition potential, time, and temperature. These cross-sectional octahedral Cu2O microcrystals exhibited high electrocatalytic activity for ethylene (C2H4) production through CO2 reduction. In a 0.1M KHCO3 electrolyte, the Faradaic efficiency for C2H4 reached 42.0% at a potential of -1.376V vs. RHE. During continuous electrolysis over 10h, the FE (C2H4) remained stable around 40%. During electrolysis, the fully exposed (111) crystal faces of Cu2O microcrystals are reduced to Cu0, which enhances C-C coupling and could serve as the main active sites for catalyzing the conversion of CO2 to C2H4.

Toward more practical site density determination in Fe-N-C catalysts for oxygen reduction reaction: NO-stripping at gas diffusion electrode setup

Evaluation of the site density of single-site iron catalysts has always been a challenge due to the complexity of those materials, and the difficulty of finding selective and simple probing methodologies. Since iron coordinating nitrogen (FeN4) is recognized as the main active site for oxygen reduction reaction (ORR), it is fundamental to develop a method to assess the content in catalysts. Several bulk-probing and surface-probing methods have been developed in the last decade each one with its pros and cons. Among others, with certain limitations, NO stripping performed at a rotating disc electrode (RDE) has become a common characterization to evaluate site density and turnover frequency of Fe-N-C due to the relatively simple procedure. At the same time, gaining information on the activity on more practical devices has brought to the spreading of gas diffusion electrodes (GDE) in half-cell configuration to mimic the cathodic compartment of a fuel cell, a leading device for those materials applications. Here we proposed a transposition of NO-stripping from RDE to GDE to evaluate the site density under more practical devices. Several parameters have been considered (i.e., pH, loading, FeN4 selectiveness) and comparisons with RDE have been done to validate the methods. A homemade Fe-N-C catalyst has been used as a benchmark and compared to Pajarito Powder catalyst and others (including metal-free) showing the validity and selectivity of the method.

A Multi‐Site Synergistic Effect in High‐Entropy Alloy for Efficient Hydrogen Evolution

AbstractUnraveling the mechanism driven by electronegativity‐dominated electronic configuration is crucial for developing high‐entropy alloys as efficient catalyst for hydrogen evolution reaction (HER). In this work, different atoms with diverse electronegativities are explored to regulate the electrocatalytic activity of PtFeCoNi@HCS toward HER, resulting in PtFeCoNiCuCr@HCS with an overpotential of 29 mV at 10 mA cm−2 and enhanced durability surpassing that of commercial 20% Pt/C in KOH environment. Based on various physicochemical and electrochemical techniques as well as density functional theory calculations, a multi‐site synergistic effect within PtFeCoNiCuCr@HCS material is elucidated in terms of both structural composition and electrocatalytic process. Briefly, Pt and Cu serve as the fundamental elements to form face‐centered cubic crystal framework, Cr primarily functions as an electron donor to regulate the electronic configuration, Co serves as the main active site for water dissociation, and the produced hydrogen species prefer to transfer toward Pt, Fe, and Cu sites for hydrogen formation. This work offers an in‐depth insight on the synergistic mechanism in high entropy alloys and is helpful for designing efficient electrocatalysts.

Droplet microreactor continuous synthesis of hierarchical Rh on CdZnS snowflakes for enhanced photocatalytic hydrogen evolution

Promising droplet microreactor-cation exchange strategy is utilized to construct the unique Rh hierarchical structure (RhHS) and Rh nanoclusters (RhNCs) on CdZnS (CZS) snowflakes. The fabricated RhHS/RhNCs/CZS achieves an optimal hydrogen evolution activity of 926.0μmol h−1 g−1, which is 5.9 and 10.5 folds enhancement that of CZS and CdS, respectively. The enhanced activity for H2 generation can be attributed to the RhHS/RhNCs (accelerating electron transfer), as well as the hierarchical structure of RhHS and CZS, which enhances reflection–absorption of visible light. Theoretical calculations reveal that Rh species can serve as new H* generation-release sites, reducing the energy barrier for hydrogen evolution. Notably, in situ Raman confirmed the Rh (Rh-H) and S (S-H) two main active sites for proton reduction during hydrogen generation. This paper provides a novel approach to constructing hierarchical structure photocatalyst (RhHS/RhNCs/CZS) for enhanced photocatalytic H2 production.

Advanced multi-component FeCoCuAlMo intermetallic electrocatalysts for efficient and sustainable hydrogen evolution in alkaline freshwater and seawater

Electrolyzing seawater to produce hydrogen is a promising sustainable energy production technology. The current non-precious metal-based hydrogen evolution reaction (HER) electrocatalysts demonstrate inadequate catalytic activity and poor stability in seawater electrolyte. Therefore, developing stable and efficient non-precious metal-based HER electrocatalysts is a major challenge for achieving sustainable green energy development. This work reports a multi-component intermetallic catalyst FeCoCuAlMo prepared by arc melting and chemical dealloying methods. The electrocatalytic hydrogen evolution performance of catalysts with varying atomic ratios (FeCoCu)20(Al70Mo30)80, (FeCoCu)30(Al70Mo30)70, (FeCoCu)40(Al70Mo30)60, and (FeCoCu)50(Al70Mo30)50 in alkaline seawater and alkaline electrolyte was studied. The findings indicate that these catalysts primarily consist of AlMo3 and (Cu0.35Fe0.35Co0.3)Al, among which the dealloyed (FeCoCu)30(Al70Mo30)70 exhibits excellent catalytic activity with overpotentials of 137.54 and 116.91 mV at a current density of 100 mA/cm2 in alkaline seawater and alkaline electrolyte, respectively, outperforming most catalysts. Additionally, it demonstrated long-term stability in alkaline seawater and alkaline electrolyte for 250 and 400 h without significant decay at overpotentials of 236 mV and 276 mV, respectively. This improved performance can be attributed to the unique structure of the multi-component intermetallic compound, which provides good thermodynamic stability and synergistic effects among its constituents, thereby enhancing HER performance. Within this multi-component intermetallic compound, AlMo3 particles serve as the primary conductive medium to accelerate electron transfer, while (Cu0.35Fe0.35Co0.3)Al serves as the main active site, resulting in a stable structure that provides the catalyst with high catalytic activity and good stability. Thus, the (FeCoCu)30(Al70Mo30)70 electrocatalyst is a promising candidate for seawater electrolysis aimed at hydrogen production.

Enhancing the Regeneration Performance of Methylene Blue Saturated Biochar in H2O2 System via Fe‐Doping

AbstractTo improve the regeneration efficiency of methylene blue (MB) saturated biochar in H2O2 system, biochar was modified by Fe‐doped by using FeSO4 and Fe(NO3)3 as iron sources. The effects of Fe‐doped on its microstructure were characterized by XRD, SEM, and BET. The adsorption and regeneration performance of biochar before and after Fe‐doped were compared through adsorption and regeneration experiments. X‐ray photoelectron spectroscopy, electron spin resonance, and quenching experiments were used to explore the regeneration mechanism. The results show that Fe‐doped biochar (SP‐GBC) prepared from FeSO4 maintains a high specific surface area of 1205.9 m2/g and a high adsorption capacity of 375.43 mg·g−1 for MB. After adsorption, the MB‐saturated SP‐GBC exhibits excellent regeneration performance in the H2O2 system, in which the regeneration efficiencies for five consecutive cycles are 85.76%, 83.92%, 94.01%, 99.24%, and 100.79%, respectively. The synergistic effect of H2O2 desorption and degradation is the main regeneration mechanism for MB‐saturated SP‐GBC. The zero valent iron and Fe (II) on the surface of SP‐GBC are the main active sites for H2O2 activation, while 1O2 and HO· are the main oxidation species. In summary, this work provides a simple and feasible method for the design and synthesis of adsorbents with highly efficient regeneration performance.

Mechanistic insights and performance evaluation of ZnFe-Modified bovine manure biochar in activating peroxymonosulfate for efficient thiamethoxam degradation: A combined DFT calculation and degradation pathway analysis

The study explored the degradation of thiamethoxam (THM) in water using modified bovine manure biochar as a catalyst for the first time, due to its potential harm to living organisms and frequent detection in natural water bodies. Experimental findings revealed that the rate constants for peroxymonosulfate (PMS)-catalyzed THM degradation by bovine manure biochar modified with ZnCl2 and K2FeO4 (ZnFeBC) increased by 76.78 times compared to unmodified biochar (BC), achieving a 100% degradation rate within 60 min. ZnFeBC exhibited excellent PMS activation performance across various pH levels. XPS characterization and Density Functional Theory (DFT) calculations have revealed that Fe element cycling occurs on the ZnFeBC surface, resulting in increased charge transfer rates at the reaction interface. The main active sites responsible for PMS activation were found to be Fe0 and Fe3O4. The degradation mechanism of THM by the ZnFeBC/PMS system involved SO4•-, •OH, 1O2 and electron transfer. This catalyst demonstrated strong pH adaptability and outstanding catalytic degradation capabilities for various pollutants, making it highly suitable for widespread wastewater treatment applications, while also providing a new way for resource reutilization of bovine manure.

Removal of aqueous oxytetracycline using copper-loaded biochar-activated peroxodisulfate: Synergistic mechanism of adsorption and nonradical 1O2

Antibiotic contamination from livestock and poultry farming wastewater has caused substantial adverse effects on the environment and humans. Therefore, in this study, bifunctional adsorption and synergistic degradation of Cu and N codoped biochar (Cu-N/BC) were utilized to efficiently promote the activation of peroxodisulfate (PDS) for removing oxytetracycline (OTC). Cu-N/BC exhibited a high adsorption affinity toward OTC. The adsorption of OTC (50 mg/L) by 0.4 g/L catalyst could reach 36.2 mg/g in 30 min, and the removal of OTC reached 97.24 % in 90 min after adding 0.5 mM PDS. Preadsorption experiments demonstrated that the OTC enriched on the Cu-N/BC surface facilitated the subsequent degradation reaction，its reaction rate constant increases from 0.026 to 0.037. Low-valent copper (Cu0/Cu+), pyridine N, and oxygen-containing functional groups (CO) were the main active sites of Cu-N/BC, and the main contribution toward OTC degradation was from the nonradical pathway of singlet oxygen. Furthermore, potential degradation pathways were revealed, and the intermediates in the OTC degradation process were identified. Cu-N/BC exhibited stable performance, a wide pH application range, and great potential for practical application. This study offers a new concept for designing a bifunctional carbon-based material to remove antibiotics from wastewater.

Uranium electrolytic deposition with regenerable Se2− active sites at low cell voltage

The electrochemical extraction of uranium from wastewater represents an effective strategy for the sustainable supply of fuel and the protection of the environmental. However, the rational design of high-efficiency electrocatalysts remains a significant challenge, largely due to the lack of research on the structure–activity relationship. In this study, we developed a novel electrocatalysis based method for the extraction of uranium in solution, combining the redox of selenium (Se2-/Se4+) and uranium extraction. This method enables the high-efficiency extraction uranium in solution, even at relatively low cell voltages of 1 V. The Co3Se4-based electrocatalyst exhibits excellent UO22+ capture properties, endowing it with an electrolytic deposition capacity of 2264 mg g−1 at the concentration of 560 mg L−1 within 48 h. Even in a low concentration uranium solution (5 mg L−1), the extraction capacity can still reach 199.2 mg g−1. X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) revealed that the main active sites of Co3Se4 were renewable Se2- sites. The absorbed UO22+ can be spontaneously reduced to the unstable U(V) intermediate by reversible electron transfer, and then re-oxidized to (UO2)O2·2H2O in the presence of hydrogen peroxide (H2O2). The significant discovery provides a novel electrochemical medium, elucidates the mechanism of the uranium extraction process, and introduces a novel strategy for harvesting U from wastewater.

Highly efficient activation of peroxymonosulfate via KOH-activated Fe@NC for the degradation of bisphenol A.

In this study, the KOH-modified Fe-ZIF-derived carbon materials (Fe@NC-KOH-x) were designed for Fenton-like systems to enhance bisphenol A (BPA) removal from wastewater. Compared with the Fe@NC without KOH activation, the pore structure, BET (Brunner-Emmet-Teller) surface area, and oxygen-containing functional group of KOH-activated Fe@NC-KOH-x are dramatically improved, which increases the adsorption and catalytic performance. The Fe@NC-KOH-900/PMS system showed significant BPA removal reactivity across wide pH ranges and low doses of Fe@NC-KOH-900. Interestingly, our findings indicated that the removal effectiveness of BPA improved when PMS was introduced following the saturation adsorption of Fe@NC-KOH-x, as compared to the simultaneous introduction of Fe@NC-KOH-x and PMS. More particularly, through regression analysis, we found that the proportion of reactive species in the Fe@NC-KOH-x/PMS system changes with the increase of pyrolysis temperature, and there was a certain relationship between structure-function and active species in the Fe@NC-KOH-x/PMS system. O-C = O, Fe-N4, C-O, and pyrrolic N in Fe@NC-KOH-x lead to the generation of •OH, and SO4-•, C = O, Fe-N4, and defect are closely related to FeIV = O, and the formation of 1O2 is affected by Fe-N4, graphite N, C = O, and defect. Also, the density functional theory (DFT) calculation and the potential correlation between catalyst active centers and reactive oxygen species indicate that Fe-N4 is the main active site of Fe@NC-KOH-x. These outcomes of the study offer an innovation for enhanced elimination of BPA in wastewater treatment and provide a dynamic understanding of the mechanism of BPA degradation.

One-step microwave-assisted synthesis of metal-free heteroatom-doped carbon catalyst for H2O2 electrosynthesis

This study reports on a one-step conversion of polyaniline into a metal-free heteroatom-doped carbon electrocatalyst through microwave heating. A high surface area carbonaceous structure forms after a total synthesis time of only 140 s, with the presence of nitrogen and oxygen functional groups, as confirmed by thorough spectroscopic analysis. This catalyst exhibits high activity (onset potential of 0.73 V vs. RHE), selectivity (82 %), and stability (over a 7.5-hour test period) for the electrochemical oxygen reduction reaction towards hydrogen peroxide in alkaline media. Microwave synthesis reduces heating time by 29-fold and energy consumption by 77-fold, while producing materials with high electrocatalytic efficiency comparable to those conventionally prepared at 700°C. The microwave and the conventionally synthesized heteroatom-doped carbon catalysts show similar electrochemical performances, which can be attributed to the presence of nearly identical nitrogen functional groups and surface area in the two samples. In contrast, the microwave and conventionally synthesized samples exhibit significant variations in their oxygen functional groups. These results suggest that nitrogen functional groups are the main active sites for alkaline hydrogen peroxide formation, while oxygen functional groups play a minor role in the catalytic activity. Our work brings a solid contribution to the debate regarding the active centers for hydrogen peroxide formation.

Beneficial utilization of ball-milled carbon sand to activate peroxymonosulfate oxidation: Quantitation of ROS using probe-based kinetic models and mechanism insights

In this study, the oil sand was treated with an integrated process of pyrolysis and ball milling, and the obtained ball-milled carbon sand (BMCS) was utilized as peroxymonosulfate (PMS) activator to treat wastewater containing aniline (AN). Quenching experiments and electron paramagnetic resonance (EPR) confirmed the existence of sulfate radical (SO4∙‐), hydroxyl radical (·OH) and singlet oxygen (O12) in the BMCS/PMS system. A probe-based kinetic model was constructed to describe the degradation process of pollutants in the BMCS/PMS system, quantified the exposure of each reactive oxygen species and their contributions to AN degradation. BMCS activated PMS to quickly produce SO4∙‐ and gradually generate ·OH. The O12 exposure showed a rapid increasing trend and the largest total exposure, while its contribution to AN degradation was small. Ball milling time and BMCS dosage demonstrated significant effect on the exposure of ·OH and O12. The main active sites for BMCS to activate PMS were iron oxides, defective carbon and oxygen-containing functional groups. This study provides a green and low-cost process for value-added transformation of pyrolytic residue of oil sand (PROS), so as to promote PROS treatment mode from harmless disposal to resource utilization.

In situ-grown nitrogen-sulfur co-doped carbon nanotubes encapsulated with FeS particles as cathode materials for zinc-air batteries

Transition metal sulfides as ideal oxygen reduction reaction (ORR) catalysts have great potential to regulate multiple reaction pathways and understand their corresponding internal reaction mechanisms at cathode in zinc-air batteries (ZABS), effectively. This work adopted a facile one-pot synthesis method based on chemical vapor deposition (CVD), which utilizes the synergistic effect of zeolite imidazolium ester skeleton (ZIF-8) and polypyrrole (PPY) to grow nitrogen-sulfur co-doped carbon nanotubes (NS-CNT) in the shape of colonic with a relatively uniform size and encapsulated with FeS nanoparticles as the main active sites. The synthesized purpose catalyst noted as FeS-NS-CNT-900, in which that the FeS nanoparticles were tightly encapsulated in carbon nanotubes, and this special structure ensures that the FeS particles do not detach during the reaction, thus greatly enhancing their electrochemical activity and stability. As expected, the FeS-NS-CNT-900 catalyst exhibited a half-wave potential of 0.877 V which is higher than that of commercial platinum charcoal (0.847 V), at 0.1 mol KOH. More importantly, the formation of abundant FeS catalytic active sites, the optimal conditions for NS-CNT growth, and the covered mechanisms of the enhanced ORR reaction activity of FeS-NS-CNT-900 were thoroughly investigated. Additionally, whileFeS-NS-CNT-900 was used as an air cathode material for the assembly of a zinc-air battery, it exhibited a peak power density and specific capacity of 123 mW cm−2 and 785.81 mA h g−1, respectively, which were significantly better than that of platinum-carbon cathode (92.8 mW cm−2 and 740.4 mA h g−1). And surprisingly, the battery with FeS-NS-CNT-900 cathode exhibited (delivered/showed) a high cycle stability of 260 h at 5 mA cm−2. Conclusively, present work provides a feasible method for in situ growth of sulfur and nitrogen co-doped carbon nanotube encapsulated transition metal sulfide nanoparticle catalysts, which may pave a new avenue for the preparation of high ORR performance air cathode material for ZABS.

Multi-polar group cationic collector HTTPD: Mechanistic insights into selective flotation of bastnaesite

To address the challenge of separating bastnaesite rare earth minerals from gangue minerals, this study independently synthesized a novel multi-polar group cationic surfactant,2,2-bis(hydroxymethyl)-N1,N1,N3,N3-tetramethyl-N1,N3-bis(3-tridecanamidopropyl)propane-1,3-diaminium bromide (HTTPD), as a collector. The flotation results showed that HTTPD could obtain REO grade of 69.71% and recovery of 89.33%, significantly outperforming conventional collectors and proving to be an excellent collector. Density functional theory (DFT) calculation displayed that two quaternary ammonium groups and –NH/OH polar groups were main active sites with strong reactivity. The quaternary ammonium groups of HTTPD strongly adsorbed on the bastnaesite surface through electrostatic attraction, thereby enhancing the flotation selectivity from calcite. The –NH/–OH polar groups adsorbed with bastnaesite by hydrogen bonding interaction. Multi-polar group synergistic adsorption, formed through electrostatic attraction and hydrogen bonding interaction, was the primary mechanism for the efficient separation of bastnaesite and calcite. This research not only provided new insight and theoretical guidance for the design and application of novel collectors but also promoted the efficient development and utilization of rare earth mineral resources.

Investigation of the efficacy of graphite-sulfur iron tailing composite catalysts for activation of peroxydisulfate for rhodamine B degradation.

Herein, a novel graphite/sulfur iron tailing composite was applied as a peroxydisulfate (PDS) activator for rhodamine B (RhB) degradation in the water. The superior catalytic efficiency of graphite/sulfur iron tailing was achieved through radical (SO4•- and •OH) and non-radical (1O2) processes according to the radical quenching experiments and electron paramagnetic resonance analysis. The carbonyl group and Fe species were the main active sites on the surface of graphite/sulfur iron tailing, which was demonstrated by combining Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and reaction kinetic experiments, and a possible degradation mechanism was also proposed. Overall, activated with 0.30g/L of C-1, PDS achieved a 94.8% removal rate for RhB and maintained a removal rate of over 85% even after five consecutive operation cycles, and this study will benefit the application of iron/carbon composite materials in practical water treatment.

One-step utilizing of waste acidic Cu-containing etching solution to prepare hierarchical Cu-ZSM-5 for efficient flue gas Hg0 removal

Developing mercury adsorbents could mitigate environmental risk of mercury pollution. In this study, waste acidic Cu-containing etching solution from PCBs etching industry was utilized for the simultaneous porosity etching and Cu/Cl sites loading to prepare WA-ZSM for Hg0 removal via a one-step method. WA-ZSM synthesized with different waste acid concentrations exhibited over 94 % Hg0 removal efficiency within 60 min. The long-term stability of 5WA-ZSM under 110 μg/m3 Hg0 within 300 min was higher than 90 %. The dealumination process significantly affected the formation of micropores and Cu loading into the pore structure. The EFAl-Al3+ and “Si-O-Cu” structures formed by dealumination greatly enhanced the strong acid sites and the Cu sites improved the medium strong acidity. Isolated [Cu-OH]+ sites and [Cu–O-Cu]2+ sites are the main active sites in Hg0 removal. This method successfully synthesizes low-cost, high-efficiency Hg0 adsorbents using hazardous wastes, presenting a significant advancement in sustainable waste utilization and mercury pollution control.

Quantum Confinement and End-Sealing Effects for Highly Sensitive and Stable Nitrogen Dioxide Detection: Homogeneous Integration of Ti3C2Tx-Based Flexible Gas Sensors.

The real-time and room-temperature detection of nitrogen dioxide (NO2) holds significant importance for environmental monitoring. However, the performance of NO2 sensors has been hampered by the trade-off between the high sensitivity and stability of conventional sensitive materials. Here, we present a novel fully flexible paper-based gas sensing structure by combining a homogeneous screen-printed titanium carbide (Ti3C2Tx) MXene-based nonmetallic electrode with a MoS2 quantum dots/Ti3C2Tx (MoS2 QDs/Ti3C2Tx) gas-sensing film. These precisely designed gas sensors demonstrate an improved response value (16.3% at 5 ppm) and a low theoretical detection limit of 12.1 ppb toward NO2, which exhibit a remarkable 3.5-fold increase in sensitivity compared to conventional Au interdigital electrodes. The outstanding performance can be attributed to the integration of the quantum confinement effect of MoS2 QDs and the conductivity of Ti3C2Tx, establishing the main active adsorption sites and enhanced charge transport pathways. Furthermore, an end-sealing effect strategy was applied to decorate the defect sites with naturally oxygen-rich tannic acid and conductive polymer, and the formed hydrogen bonding network at the interface effectively mitigated the oxidative degradation of the Ti3C2Tx-based gas sensors. The exceptional stability has been achieved with only a 1.8% decrease in response over 4 weeks. This work highlights the innovative design of high-performance gas sensing materials and homogeneous gas sensor techniques.

In-Depth Investigation of Role of -BCO2 in the Degradation of Sulfamethazine by Metal-Free Biochar/Persulfate: The Mechanism of Occurrence of Nonradical Process.

The remediation of organic wastewater through advanced oxidation processes (AOPs) based on metal-free biochar/persulfate systems has been extensively researched. In this work, boron-doped alkali lignin biochar (BKC1:3) was utilized to activate peroxymonosulfate (PMS) for the removal of sulfamethazine (SMZ). The porous structure and substantial specific surface area of BKC1:3 facilitated the adsorption and thus degradation of SMZ. The XPS characterization and density functional theory (DFT) calculations demonstrated that -BCO2 was the main active site of BKC1:3, which dominated the occurrence of nonradical pathways. Neither quenching experiments nor EPR characterization revealed the generation of free radical signals. Compared with KC, BKC1:3 possessed more electron-rich regions. The narrow energy gap (ΔEgap = 1.87 eV) of BKC (-BCO2) promoted the electron transfer to the substable complex (BKC@PMS*) on SMZ, driving the electron transfer mechanism. In addition, the adsorption energy of BKC(-BCO2)@PMS was lower (-0.75 eV → -5.12 eV), implying a more spontaneous adsorption process. The O-O (PMS) bond length in BKC(-BCO2)@PMS increased significantly (1.412 Å → 1.481 Å), which led to the easier decomposition of PMS during adsorption and facilitated the generation of 1O2. More importantly, a combination of Gaussian and LC-MS techniques was hypothesized regarding the attack sites and degradation intermediates of the active species in this system. The synergistic T.E.S.T software and toxicity tests predicted low or even no toxicity of the intermediates. Overall, this study proposed a strategy for the preparation of metal-free biochar, aiming to inspire ideas for the treatment of organic-polluted wastewater through advanced oxidation processes (AOPs).

Synergistic catalysis of NO and chlorobenzene over Mn3O4-CeO2 catalysts: Acid sites, catalytic pathway and mechanism

Catalyst active sites and surface acidity are crucial for the synergistic catalysis of NOx and dioxins, determining the selectivity towards N2 and CO2. This study synthesized Mn3O4-CeO2 catalysts to investigate the influence of these sites on the catalytic performance for NO and chlorobenzene. Mn0.086Ce, made by the redox method, showed the highest Mn-Ce interface, achieving nearly complete conversion of chlorobenzene and NO at 180℃, with CO2 and N2 selectivity reaching about 80 % and 100 %, respectively. EPR, NH3-TPD and Py-IR analyses revealed that the Mn-Ce interface induces the formation of Lewis acid sites and oxygen vacancies, facilitating the adsorption and conversion of chlorobenzene, NH3, and NO. Mn adjacent to Lewis acid sites is the main active site, while Ce acts as an electron transfer agent. Based on the results of in-situ DRIFTS and TOF-SIMS, the possible degradation pathway for chlorobenzene was proposed and as follows: phenol, benzoquinone, maleic anhydride, propionic acid, CO2, and H2O. The NH3-SCR reaction follows the Eley-Rideal mechanism at 150–300℃.

Biochar with root pore channels loaded copper cobalt bimetallic metal organic framework for effective peroxomonosulfate activation to degrade organic pollutants

Biochar (BC) with root pore channel structure was used as the carrier, and bimetallic organic framework (CuCo-MOF) as the main active site. The CuCo-MOF was successfully dispersed in the internal channels of BC by in situ reaction, forming a composite catalyst (BC/CuCo-MOF(10 %)) with unique reaction channels. The degradation efficiency of ciprofloxacin (20 mg/L) in only 25 min was 96.4 %, and its catalytic performance was superior to that of the single BC and CuCo-MOF. On the one hand, abundant CuCo-MOF reaction sites were distributed in the relatively closed porous reaction channel of BC, which accelerated the mass transfer process (short mass transfer distance) during the CIP degradation process and improved the CIP degradation performance. On the other hand, highly conductive BC facilitates electron transfer between Cu2+/Cu+ species and HSO5-, accelerating the redox cycle of Cu2+/Cu+, thereby improving catalytic activity. Besides, the composite catalyst was still able to achieve a degradation efficiency of 87.6 % for CIP after five cyclic degradation experiments. The concentrations of Cu and Co ions in the reaction solution were only 0.04 and 0.03 mg/L. Therefore, the composites have excellent catalytic activity and stability. Both non-radical 1O2 and radicals (SO4·- and ·OH) were involved in the reaction, and the non-radical 1O2 pathway played a dominant role in the CIP degradation process.