PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2024
·Vol. 121
·期 3
·e2313387121
·
IF 9.4
Jirui Guo,Yujie Wang,Yanan Shang,Kexin Yin,Qian Li,Baoyu Gao,Yanwei Li,Xiaoguang Duan,Xing Xu
The studies on the origin of versatile oxidation pathways toward targeted pollutants in the single-atom catalysts (SACs)/peroxymonosulfate (PMS) systems were always associated with the coordination structures rather than the perspective of pollutant characteristics, and the analysis of mechanism commonality is lacking. In this work, a variety of single-atom catalysts (M-SACs, M: Fe, Co, and Cu) were fabricated via a pyrolysis process using lignin as the complexation agent and substrate precursor. Sixteen kinds of commonly detected pollutants in various references were selected, and their lnkobs values in M-SACs/PMS systems correlated well (R2 = 0.832 to 0.883) with their electrophilic indexes (reflecting the electron accepting/donating ability of the pollutants) as well as the energy gap (R2 = 0.801 to 0.840) between the pollutants and M-SACs/PMS complexes. Both the electron transfer process (ETP) and radical pathways can be significantly enhanced in the M-SACs/PMS systems, while radical oxidation was overwhelmed by the ETP oxidation toward the pollutants with lower electrophilic indexes. In contrast, pollutants with higher electrophilic indexes represented the weaker electron-donating capacity to the M-SACs/PMS complexes, which resulted in the weaker ETP oxidation accompanied with noticeable radical oxidation. In addition, the ETP oxidation in different M-SACs/PMS systems can be regulated via the energy gaps between the M-SACs/PMS complexes and pollutants. As a result, the Fenton-like activities in the M-SACs/PMS systems could be well modulated by the reaction pathways, which were determined by both electrophilic indexes of pollutants and single-atom sites. This work provided a strategy to establish PMS-based AOP systems with tunable oxidation capacities and pathways for high-efficiency organic decontamination.
研究领域:
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Lipeng Wu,Xiaomin Wang,Pengwei Zhao,Yongsheng Ji,Bin Li,Yongsheng Xu,Tao Liao,Qing Xia,Yang Li,Xiaobin Fan,Wenchao Peng
Atomic Zn-N-C materials are synthesized by direct carbonization of ZIF-8, which maintains the rhombic dodecahedron morphology (RDM) with abundant nanopores. Zn-N-C-RDM shows enhanced catalytic activity with bisphenol A (BPA) as model pollutant and peroxydisulfate (PDS) as oxidant. Molecular dynamic (MD) calculations show that mean square displacement (MSD) of PDS, BPA, and H 2 O molecules in the nanotunnels decreases obviously with smaller pore size. Due to the confinement, the BPA ( d i = 1.0 nm) and PDS ( d i = 0.5 nm) can easily enter and confined in the cavities of Zn-N-C-RDM. PDS can be therefore activated more easily to degrade BPA due to their faster diffusion and shorter transfer routes. > 97 % degradation of BPA can therefore be achieved by Zn-N-C-RDM within 20 min. Quenching experiments, electron paramagnetic resonance (EPR) and open circuit potential (OCP) results indicate that O 2 •− radical dominate the degradation. According to the density functional theory (DFT) results, the binding sites of Zn-pyridinic N are the main active sites. This work provides new insights for improving activity in Fenton-like reactions in the field of environmental remediation.
研究领域:
环境科学
·
催化材料
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
CHEMOSPHERE
·
2021
·
IF 7.086
Xingchen Yang,Guoce Yu,Lejin Xu,Jianlong Wang
The treatment and disposal of spent radioactive organic solvents, i.e., tributyl phosphate (TBP) and diluent (such as kerosene, n -dodecane, etc.), produced in the reprocessing of spent fuel in the closed cycle are crucial for the sustainable development of the nuclear industry. In this study, the synthesized nanoscale zero-valent iron (nZVI) was used as the heterogeneous Fenton-like catalyst to promote the generation of hydroxyl radicals (•OH) by reacting with H 2 O 2 to degrade the mixed organic solvents of TBP and n -dodecane. nZVI was characterized by scanning electron microscopy (SEM), nitrogen adsorption/desorption isotherms, and X-ray photoelectron spectroscopy (XPS) to investigate the micro-morphology, nano-particle size, and surface valence state. The change of Fe 2+ /Fe 3+ concentration ratio during the reaction was measured to clarify the performance of nZVI. The effects of temperature, catalyst dosage, H 2 O 2 dosage, and acidifier concentration on the degradation of TBP and n -dodecane were studied, and the results were complemented by the COD of the aqueous solution and the volume reduction rate of the organic phase. The mixed organic solvents of TBP and n -dodecane containing Co 2+ were used to simulate the spent radioactive organic solvents and to study the distribution of nuclides after the reaction. The results showed that most of the radioactivity was in the residual solution, and the condensate contained almost no radioactivity. The degradation of TBP and n -dodecane was carried out separately, which showed that n -dodecane was more difficult to degrade. Density functional theory (DFT) calculations were applied to determine the adsorption energy of organic solvents and nZVI. According to the Fourier transform infrared spectra (FTIR) and their corresponding DFT calculations, liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) of the sample after the reaction, the possible intermediates were analyzed, and the degradation mechanism was speculated.
研究领域:
环境科学
·
核化学与放射化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Yuanzheng Zhang,Xiang Chen,Chao Liang,Lifeng Yin,Yang Yang
This study develops an advanced single-atomic iron-loaded graphitic carbon nitride (Fe 1 /CN) with unparalleled efficiency for converting peroxymonosulfate (PMS) to oxidants for water treatment. We found that acid-etching of Fe 1 /CN leads to the reconstruction of conventional Fe 1 –N 4 to Fe 1 –C 2 N 1 active sites. The acid-induced Fe 1 –C 2 N 1 sites are more favorable for PMS binding and have a lower energy barrier for 1 O 2 production. The precise tuning of the coordination environment bestows the acid-etched Fe 1 /CN with 29 times higher rate constants of bisphenol A degradation than its pristine counterparts. Further, the particulate catalysts were assembled into a self-supported catalytic membrane, which demonstrates excellent long-term durability throughout 170 h flow-through tests in both synthetic and real wastewater . This work provides pivotal insights into improving PMS activation activity by regulating the coordination environment around single atomic Fe sites. The engineering innovation laid the groundwork for new point-of-use water treatment devices.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Xinhao Wang,Zhaokun Xiong,Hongle Shi,Zelin Wu,Bingkun Huang,Heng Zhang,Peng Zhou,Zhicheng Pan,Wen Liu,Bo Lai
Rationally regulating reaction mechanisms in Fenton-like reactions by tuning the properties of catalysts is of great significance, but still challenging. Herein, we synthesized various active center size-dependent catalysts to realize the switching of reaction mechanisms and pollutant degradation routes in peroxymonosulfate (PMS) activation systems. The results illustrated that the reaction mechanism transformed from radical oxidation (51.64%) to nonradical oxidation (89.92%) with the decrease of active center size from nanoparticle (Co NP -NC) to single atom (Co SA -NC). The evolution of reactive species switched the degradation intermediates and pathway of sulfisoxazole (SIZ). The generation of singlet oxygen ( 1 O 2 ) in Co SA -NC/PMS tends to selectively attack electron-rich site of SIZ, while reaction between radicals and SIZ prefers non-selective oxidation in Co NP -NC/PMS system. Besides, the toxicity tests indicated that the conversion from non-selective to selective oxidation resulted in lower toxicity of effluent after reaction, which can further reduce environmental risks of effluent.
研究领域:
环境科学
·
催化化学
·
污染控制
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Lu Xu,Xiaojia Wei,Yuetong Qi,Wei Qiao,Juan Shi,Yabo Shang,Keqian Li,Xin Jin,Xue Bai,Xuan Shi,Pengkang Jin
The activation of persulfate (PS) in dissolved organic matter (DOM) solution using visible light has demonstrated potential for advanced wastewater treatment. This study presents a novel visible light-assisted homogeneous Fenton-like process (DOM-Fe 3+ -PS-Vis) for the efficient DOM degradation, based on the ligand-to-metal charge transfer (LMCT)-induced enhanced Fe 3+ reduction and PS activation. The simultaneous addition of Fe 3+ and PS to DOM-enriched solutions under visible light significantly improved PS activation, leading to the degradation of DOM and coexisting organic contaminants. The PS decomposition rate constant in the DOM-Fe 3+ -PS-Vis process was calculated to be 3.5–20.69 times higher than that of the DOM-PS-Vis, Fe 3+ -PS-Vis, and DOM-Fe 3+ -PS-Dark systems. Notably, over half of the decomposed PS in the DOM-Fe 3+ -PS-Vis process was activated by Fe 2+ generated via the LMCT between DOM and Fe 3+ . SO 4 − and OH were identified as the dominant reactive species present in the DOM-Fe 3+ -PS-Vis process with the steady-state concentration of 1.63–4.11 × 10 −13 M and 0.07 × 10 −13 M, respectively, which were 2.4–81.5 and 0.5–7 times higher than those in the DOM-PS-Vis, Fe 3+ -PS-Vis, and DOM-Fe 3+ -PS-Dark systems. Additionally, hydrophobic components with more aromatic carbon in DOM were found to promote the catalytic performance of the DOM-Fe 3+ -PS-Vis process. This study highlights the efficiency and promise of LMCT-induced enhanced Fe 3+ reduction and PS activation in DOM-enriched solutions under visible light for advanced wastewater treatment.
研究领域:
环境科学
·
废水处理
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ENVIRONMENTAL MANAGEMENT
·
2025
·
IF 8.4
Bo Cai,Shuiping Ouyang,Jingyao Fan,Chao Liu,Yongjian Zhang,Zechang Wei,Zhinan Wang,Xuechun Wang,Hong Lei
With the overuse of antibiotics, the aquatic environment has been heavily polluted, which has serious negative impacts on various organisms. AOPs degradation system is a promising treatment approach for wastewater of antibiotics. Herein, an efficient, stable and low-cost Fe, N co-modified biochar derived spent coffee ground was developed for activation of PMS to remove TC. 1Fe1N-C-800 biochar provided a 100 % removal rate of TC (50 mg/L) within 30 min at room temperature, which was higher than 1Fe-C-800 (73 %) and 1N-C-800 (40 %). Meanwhile, EPR and quenching experiments indicated that • O 2 − , • OH, • OH/SO 4 •- and 1 O 2 radicals were oxidized species, where the • O 2 − provided the greater contribution during the reaction. Furthermore, the possible PMS activation mechanism and degradation pathway of TC were proposed. Moreover, the Fe, N co-modified biochar showed high activity and stability at broad-pH conditions, and also a broad-spectrum ability to remove various organic pollutants. This study developed an approach for the preparation of highly efficient and stable modified biochar and supplied a sustainable choice for antibiotic wastewater treatment.
研究领域:
环境科学
·
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Libo Zhang,Lianxiang Qiu,Qingyao Zhu,Xiong Liang,Jingxiong Huang,Mengting Yang,Zhenxuan Zhang,Jiang Ma,Jun Shen
Water disinfection would result in unintended formation of halogenated disinfection by-products (DBPs) which pose potential harm to human health. In present work, Fe 78 Si 9 B 13 amorphous ribbons (Fe-Si-B AR ) showed excellent catalytic degradation performance towards an aromatic DBP, 3,5-dichlorosalicylic acid (3,5-DiClSA) by Fenton-like reaction. The catalytic degradation performances of Fe-Si-B AR , Fe 78 Si 9 B 13 crystalline ribbons (Fe-Si-B CR ) and iron powders towards 3,5-DiClSA were compared, and Fe-Si-B AR (0.0166 min −1 ) showed the fastest degradation rate. The faster surface mobility of Fe-Si-B AR , which made it easy for Fe 2+ to be oxidized by H 2 O 2 , facilitated the degradation process. High-valent iron of Fe IV could be generated which accounted for degradation of 3,5-DiClSA. The Fe-Si-B AR also showed better and better catalytic performance in 10 reuse cycles. Besides, the cytotoxicity tests indicated that the overall toxicity level of 3,5-DiClSA was declined by 88.1 % after degradation by Fe-Si-B AR . Our results showed that Fe-Si-B AR is a promising catalyst for the degradation of aromatic DBPs.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2021
·
IF 10.588
Feng Cheng,Peng Zhou,Xiaowei Huo,Yang Liu,Yongli Zhang
In this study, Fenton-like chain reaction is constructed by coupling nanoscale tungsten powders (nW 0 ) and peroxydisulfate (PDS). The nanoscale tungsten powders/peroxydisulfate (nW 0 /PDS) system exhibits a high oxidation efficiency toward diverse pollutants and expands the effective pH range up to 9.8. Results reveal • OH and sulfate radical (SO 4 •− ) were confirmed to be responsible for 4,4′-ethylidenebisphenol (EBP) degradation, especially • OH. The corrosion process of nW 0 results in the in-situ production of H 2 O 2 and the transient-state tungsten species (W (x, x < VI)), initiating the reaction of H 2 O 2 and tungsten species to generate • OH. PDS can accelerate nW 0 corrosion to enhance the Fenton-like reaction, and can be activated by tungsten species (nW 0 and W (x, x < VI)) to produce • OH and SO 4 •− . Integrated the analysis results of LC-QTOF-MS/MS, EBP degradation pathways were proposed. This study reveals the high oxidation efficiency over a wide pH range in the nW 0 /PDS system and provides new insight into the tungsten species induced Fenton-like reaction.
研究领域:
环境科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2014
·
IF 6.007
Xingfa Li,Xin Liu,Lili Xu,Yuezhong Wen,Jianqing Ma,Zucheng Wu
Heterogeneous Pd catalytic Fenton-like systems with in-situ-generated H 2 O 2 have recently gained significant attention for wastewater treatment. Intense research efforts have been focused on developing highly efficient Fenton-like catalysts. It is known that nanoparticle size and appropriate coordination of active compositions are important for the fabrication of a highly efficient multicomponent catalyst. Unfortunately, effects of these factors on Fenton-like reaction are still unknown. To decipher the puzzle, we designed multicomponent Pd/PdO/Fe 2 O 3 nanoparticles in SBA-15 (denoted as FePd-SBA) as a Fenton-like catalyst which possesses uniform and highly dispersed nanoparticles (small size about 5 nm) in space-confined channels of SBA-15. The fabricated catalyst shows high catalytic activities in Fenton-like reaction for dye degradation. For example, 98.6% removal of dye Acid Red 73 was obtained under in-situ generation of hydrogen peroxide. In contrast, when the catalyst loaded on SiO 2 without channels or pores (FePd–SiO 2 ) was prepared, and compared with FePd–SBA, FePd–SiO 2 showed noticeably poor performance (51.6%) under same conditions. Obviously, such a difference in results is due to the confinement effect of SBA-15 porous channels. It was also found that Fe and Pd played important roles in the synergistic effect, that is, Pd worked in in-situ H 2 O 2 generation and Fe species worked in decompose H 2 O 2 to degrade organic pollutants. When we applied this catalyst for Fenton-like reaction with addition of H 2 O 2 , it was also found that Pd and PdO played important roles and the synergistic effect between Fe and Pd species actually existed in dye removal. The unique nanostructure makes the catalyst to be a novel and welcoming choice for H 2 O 2 favorite reactions.
研究领域:
环境科学
·
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CARBON
·
2023
·
IF 10.9
Yang Zhao,Biao Ma,Xiaomei Liu,Ning Li,Yang Li,Xiaobin Fan,Wenchao Peng
Recently, single atomic metals supported on carbon materials have attracted great interests because of their high catalytic activity and stability in peroxymonosulfate (PMS)-based Fenton-like process. Herein, we propose a convenient strategy to synthesize Co single atoms supported on nitrogen-doped carbon spheres (Co@MNC) via microwave treatment. The microwave irradiation can simultaneously induce the formation of carbon defects and immobilize the Co single atoms in N doped carbon support in a few minutes. The obtained Co@MNC can activate PMS for efficient catalytic oxidation of organic pollutants. The radical quenching tests and electron paramagnetic resonance (EPR) verify that Co (IV)-oxo species, 1 O 2 , and O 2 •− are responsible for the remediation of organic pollutants. Density functional theory (DFT) calculations confirm that unique and low coordinated Co–N 2 on void or edge defects are favorable for PMS adsorption. The electrons will then transfer from Co atoms to adsorbed PMS via the bonded N. Co (IV)-oxo species and other ROSs are therefore generated for pollutants degradation. This work provides a fast method for the synthesis of single atom catalysts for efficient Fenton-like reactions.
研究领域:
环境科学
·
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CERAMICS INTERNATIONAL
·
2020
·
IF 3.83
Luo Huang,Yuan Yu,Dongfeng Sun,Fangyou Meng,Li Li,Mengfan Niu,Xiang Bi,Songmin Lin,Wenhui Chu,Bingshe Xu
In this work, we applied the fenton-like reaction to fabricate TiO 2 nanocrystalline , and employed molecular self-assembly with TiO 2 and BiOCl to form composite photocatalyst with cookie-like nano-heterostructure for enhanced solar energy to hydrogen. The TiO 2 @BiOCl photocatalyst with cookie-like nano-heterostructure exhibited excellent photocatalytic performance for the photocatalytic hydrogen evolution under sunlight irradiation compared to the single TiO 2 or BiOCl. Besides, the TiO 2 @BiOCl photocatalyst displayed outstanding reusability and stability in the photocatalytic reaction. Meanwhile, the possible mechanisms of cookie-like nano-heterostructure formation and photocatalytic redox reaction have been proposed. What's more, this work demonstrated a new perspective for the design and mass preparation of TiO 2 -based composite photocatalytic materials at atmospheric condition, which demonstrated that this method has enormous potential to achieve mass preparation of efficient photocatalyst for photocatalytic application.
研究领域:
材料科学
·
光催化技术
·
能源转换
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）