CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Ting Yang,Shisuo Fan,Yang Li,Qi Zhou
A high-efficient iron-based heterogeneous catalyst is desired to active peroxymonosulfate (PMS). Due to a large catalytic contribution of atomically dispersed Fe-N x sites, single-atom iron–nitrogen-carbon catalysts exhibit superior performance in the catalytic activation of PMS. Herein, a sequence of Fe-N-C SACs with atomically dispersed Fe-N x sites, Fe SA -N-C and Fe SA -N/C, were prepared from Fe-doped ZIF-8 and FePc@ZIF-8, respectively. Single-atom Fe-N x sites were confirmed to be the main active sites for PMS activation. Fe SA -N/C-20 with a higher density of Fe-N x sites exhibited superior catalytic performance to N/C, Fe SA -N-C, Fe SA -N/C-15, and Fe SA -N/C-25 for BPA degradation. Integrated with chemical quenching experiments, electron spin resonance (ESR), in-situ Raman spectra, and electrochemical analysis, a nonradical pathway was demonstrated to dominate the degradation of BPA in the PMS + Fe SA -N/C-20 system. More importantly, the nature of this nonradical pathway was found to be an electron-transfer regime instead of a high-valent iron or singlet oxygenation process. The BPA was adsorbed onto the Fe-N x site by a “donor–acceptor complex” mechanism to form a nonradical PMS* intermediate during the process. Benefiting from this mechanism, the PMS + Fe SA -N/C-20 system showed wide pH adaptation and high resistance to inorganic anions.
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Weile Li,Mengzhu Li,Huai Liu,Wenlong Jia,Xin Yu,Shuai Wang,Xianhai Zeng,Yong Sun,Junnan Wei,Xing Tang,Lu Lin
The economic and highly efficient synthesis of γ-valerolactone (GVL) is being increasingly focused due to its wide applications in solvent, chemical, and fuel. Herein, a range of SAPO-34 supported zirconium phosphate (ZPS-X) catalysts were prepared for a facile one-pot conversion of furfural (FF) to GVL through a series of cascaded reactions involving transfer hydrogenation, etherification, alcoholysis and esterification. The introduction of zirconium phosphate renders the formation of relatively strong Lewis acid sites, and the amount of Lewis (L) and Brønsted (B) acid sites of ZPS-X catalysts could be modified by adjusting the molar ratio of Zr to P (Zr/P ratio). Specifically, ZPS-1.0 having an appropriate Zr/P ratio with relatively strong L acid sites exhibited superior activity and selectivity for the production of GVL from FF.
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Wentao Zhang,Wenguang Huang,Jiyuan Jin,Yonghai Gan,Shujuan Zhang
The importance of singlet oxygen ( 1 O 2 ) in synthesis of fine chemicals, inactivation of viruses and bacteria, degradation of pollutants, and photodynamic therapy has promoted the research on photocatalytic generation of 1 O 2 . Metal-organic frameworks (MOFs), owing to the tunable structure, are good candidate photocatalysts for 1 O 2 generation. However, due to the poor visible-light absorption capacity and the invalid recombination of charge carriers, the 1 O 2 generation yields of most MOFs are still limited. Here, we demonstrate that β -diketone anchoring could improve the photocatalytic generation of 1 O 2 by MIL-125 through enhanced energy transfer. The enhanced energy transfer was attributed to both the narrowed bandgap and the diketone-derived oxygen vacancies, which function as the trapping sites for charge carriers. The results here shed light on the generation of 1 O 2 by visible-light-responsive MOFs and provide a new strategy for the design of MOFs-based photocatalysts.
✓ 已验证
产品关联
DOI
高影响因子
Bioactive Materials
·
2021
·
IF 14.593
Jie Yu,Sha Liu,Yupeng Wang,Xidong He,Qingfei Zhang,Yanxin Qi,Dongfang Zhou,Zhigang Xie,Xiaoyuan Li,Yubin Huang
The combination of tumor ablation and immunotherapy is a promising strategy against tumor relapse and metastasis. Photothermal therapy (PTT) triggers the release of tumor-specific antigens and damage associated molecular patterns (DAMPs) in-situ. However, the immunosuppressive tumor microenvironment restrains the activity of the effector immune cells. Therefore, systematic immunomodulation is critical to stimulate the tumor microenvironment and augment the anti-tumor therapeutic effect. To this end, polyethylene glycol (PEG)-stabilized platinum (Pt) nanoparticles (Pt NPs) conjugated with a PD-L1 inhibitor (BMS-1) through a thermo-sensitive linkage were constructed. Upon near-infrared (NIR) exposure, BMS-1 was released and maleimide (Mal) was exposed on the surface of Pt NPs, which captured the antigens released from the ablated tumor cells, resulting in the enhanced antigen internalization and presentation. In addition, the Pt NPs acted as immune adjuvants by stimulating dendritic cells (DCs) maturation. Furthermore, BMS-1 relieved T cell exhaustion and induced the infiltration of effector T cells into the tumor tissues. Thus, Pt NPs can ablate tumors through PTT, and augment the anti-tumor immune response through enhanced antigen presentation and T cells infiltration, thereby preventing tumor relapse and metastasis.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2021
·
IF 9.028
Wei Wu,Shishu Zhu,Xiaochen Huang,Wei Wei,Chao Jin,Bing-Jie Ni
Persulfate (PS) activation on biochar (BC) is a promising technology for degrading the aqueous organic contaminants. However, the complexity of activation mechanisms and components in biomass that used to produce BC makes it difficult to predict the performance of PS activation. In this study, we employed eight sludges as the representative biomass that contained absolutely different organic or inorganic components. Results showed that the elemental composition, surface properties, and structures of the sludge-derived BCs (SBCs) clearly depended on the inherent components in the sludges. The intensities of persistent free radicals (PFRs) in the electron paramagnetic resonance (EPR) correlated positively with N-containing content of sludges as electron shuttle, but negatively with the metal content as electron acceptor. Linking with PFRs as crucial sites of triggering a radical reaction, a poly-parameter relationship of predicting PS activation for organic degradation using the sludge components was established (kobs,PN = 0.004 × Cprotein + 0.16 × CM–0.895 −0.118). However, for the PS activation on those SBCs without PFRs, this redox process only relied on the sorption or conductivity-related characteristics, not correlating with the content of intrinsic components in biomass but with pyrolysis temperatures. This study provided insightful information of predicting the remediation efficiency of PS activation on BCs and further understanding the fate of contaminants and stoichiometric efficiency of oxidants in a field application.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2021
·
IF 10.588
Mengfei He,Peng Zhao,Ran Duan,Shengjun Xu,Gong Cheng,Mengjia Li,Shuanglong Ma
In this study, chitosan, a low-price and easily obtainable natural polymerized sugar containing abundant nitrogen element, was employed as a precursor for preparing hierarchically porous carbon (PC) to activate peroxymonosulfate (PMS). The PC fabricated at 800 °C obtained the optimum catalytic performance with complete removal of p-hydroxybenzoic acid (HBA) in 30 min. The selective degradation toward phenolic pollutants with different substituent groups and the resistance over the interference of typical anions and natural organic matter implied a non-radical pathway contributed most for HBA degradation. The investigation of structure-activity relationship suggested a positive linear correlation between graphitic N content and HBA removal. The chemical quenching experiment and electron paramagnetic resonance (EPR) excluded the crucial role of radicals and 1 O 2 . Solid evidence based on electrochemical techniques demonstrated the essential contribution of electron transfer pathway achieved by three successive processes including the first close adsorption of PMS by PC800 to form metastable intermediates, then an internal electron transfer from active graphitic N to PMS within metastable intermediates and finally external electron transfer from HBA to metastable intermediates. This study provided insightful mechanism understanding of a promising organics elimination strategy by PMS activation through N-doped carbonaceous materials utilizing chitosan as a simultaneous carbon and nitrogen precursor.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Li Chen,Tahir Maqbool,Congyu Hou,Wanyi Fu,Xihui Zhang
In recent years, activation of persulfate via Mn-based composites has gained interest due to extraordinary kinetics and performance for the degradation of organic contaminants. However, the potential of pristine manganese oxides (Mn 3 O 4 ) in removing organic compounds and its mechanism has not been comprehensively explored yet. This study systemically investigated the Mn 3 O 4 based peroxymonsulfate (PMS) activation to effectively mitigate bisphenol A (BPA) in different real water matrixes. Substantial mineralization (75.9%) with efficient removal of BPA (96.7%) has been achieved at optimum conditions in 60 min. A long-term performance, eight cycles of reusability, has shown merely an 11% reduction in BPA removal, highlighted the higher stability of Mn 3 O 4 . The oxidizing contributions of reactive oxygen species (ROS) were in the order of 1 O 2 > O 2 •- > SO 4 •- > • OH. The different water matrixes have influenced BPA degradation by<10%. Linear changes in BPA aromatic contents were recorded using log-transformed ultraviolet (UV) spectra and fluorescence excitation-emission matrix (EEM). Total 17 transformation products (TPs) were detected in Mn 3 O 4 /PMS/BPA system, with 13 decreasing concentrations and 4 TPs in increasing concentration with the β-scission reaction as the main pathway for the degradation of BPA. The toxicity of BPA after degradation was also significantly suppressed measured by the activated sludge inhibition method.
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Xin Chen,Ming Zhang,Haowei Qin,Jiancheng Zhou,Quanhao Shen,Ke Wang,Wenshuai Chen,Maochang Liu,Naixu Li
The perovskite-type LaFeO 3 serves as a promising photo-Fenton-like catalyst, but its low adsorption ability and catalytic activity inhibit the effective removal of ofloxacin. Herein, the LaFeO 3 and lignin-biochar composites were fabricated by a facile sol–gel pyrolysis route. As compared with LaFeO 3 nanoparticles, the LaFeO 3 /lignin-biochar composites showed better adsorption and degradation ability due to the synergistic effect between LaFeO 3 nanoparticles and lignin-biochar. Compared with LaFeO 3 , the adsorption capacity of LaFeO 3 /lignin-biochar for ofloxacin increased from 0.72 to 30.4 mg·g −1 . Importantly, this catalyst exhibited the improved degradation efficiency of ofloxacin during 75 min (95.6 % for LaFeO 3 /lignin-biochar Vs 53.4 % for LaFeO 3 ) as the adsorption process was combined with the photo-Fenton-like process. Notably, the lignin-biochar in the LaFeO 3 /lignin-biochar composites decreased the bandgap of LaFeO 3 nanoparticles from 2.10 eV to 1.79 eV due to the interface interaction between LaFeO 3 and lignin-biochar, facilitating the enhanced photo-Fenton-like activity. The hydroxyl radicals that were generated in the photo-Fenton-like process effectively induced the oxidative degradation of ofloxacin, which was confirmed by free radical capture experiments and ESR characterization. Moreover, the photo-Fenton-like degradation pathway of ofloxacin was proposed according to LC-MS analyses, and the toxicity analysis of degradation intermediates was further carried out. Hence, the LaFeO 3 /lignin-biochar composite was a promising photo-Fenton-like catalyst to eliminate ofloxacin via coupling of adsorption and photo-Fenton-like processes.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Xiaona Dong,Xiaoxue Yang,Sheng Hua,Ziqian Wang,Tianming Cai,Canlan Jiang
The continuous accumulation of triphenyl phosphate (TPHP) in soil poses a potential threat to human health. Persulfate-based advanced oxidation processes (SR-AOPs) are promising soil remediation technologies. Naturally occurring soil constituents could interact with persulfate (PS) during soil remediation by SR-AOPs. However, the production and transformation of reactive oxygen species (ROS) by synthetic reactions between PS and different soil constituents, as well as their roles in the pollutants degradation, are still largely unknown. This study systematically investigated the generation of ROS and their roles in degradation of TPHP in soil constituents activated PS process and in soil constituents-heat (50 °C) co-activated PS process. Comprehensive studies including ROS identification, electron paramagnetic resonance analysis, and ROS-generated model systems were carried out. An appreciable degradation rate of TPHP (~21.9%) in soil-PS system and the significant discrepancy in degradation rate (69.0–97.0%) in heat-soil-PS systems with three different soils suggested that soil constituents exhibited complex effects on the activation of PS. The Fe/Mn-minerals in soil effectively activated PS and facilitated TPHP degradation. Specially, the iron redox cycle (Fe(II) ↔ Fe(III)) plays a key role in ROS generation. Small molecular soil organic matter (SOM) rapidly consumed the produced ROS which led to their mineralization, while the remaining macromolecular SOM became more hydrophilic by interaction with ROS. SO 4 •− , •OH, and 1 O 2 played major roles directly in TPHP degradation, while O 2 •− could not degrade TPHP directly but might promote TPHP degradation by reducing Fe(III)- to Fe(II)-minerals or converting to other ROS. This study provides new and deeper insights into the interaction between PS and soil constituents and their roles in organic pollutant degradation in contaminated soil using SR-AOPs.
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2021
·
IF 3.605
Lincai Peng,Xueying Gao,Yao Liu,Junhua Zhang,Liang He
Alkyl levulinate as one kind of fuel additive and versatile biomass-based platform molecule has attracted significant interests in the field of sustainable chemistry, which can be harvested straight from furfural (FAL), an important industrial chemical derived from agricultural residues. The development of a high-efficiency and low-cost catalytic system is highly desirable toward this challenging valorization process. In this contribution, bifunctional zirconia-zeolite-supported heteropoly acid catalysts with adjustable Lewis and Brønsted acid sites were successfully designed via an in situ synthetic method and attempted to couple transfer hydrogenation and alcoholysis for one-pot conversion of FAL to alkyl levulinate. The catalyst characterization and catalytic behavior were systematically combined for insight into the structure–function relationship and reaction mechanism. Selectivity toward alkyl levulinate was found to be strongly dependent upon the distribution of acid sites. As-prepared HPMo(20)/Zr-MCM-41 with a Si/Zr molar ratio of 60 and H3[P(Mo3O10)4] (HPMo) impregnation concentration of 20 g/L was uniquely effective using isopropanol as a hydrogen donor and reaction medium, leading to a high isopropyl levulinate yield of 79.6%. This monolithic catalyst exhibited good stability and could be reused at least 5 times without any substantial change in the product yield after plain thermal regeneration.
✓ 已验证
产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2021
·
IF 8.001
Ruoqing Wang,Feng Shen,Yiwei Tang,Haixin Guo,Richard Lee Smith,Xinhua Qi
Levulinic acid in high yields (90%) was produced from hemicellulose-derived furfuryl alcohol catalyzed by a uniform, dandelion-like, SO 3 H-modified silica nanoflower solid acid (SiNF–SO 3 H). The SiNF–SO 3 H catalyst was prepared by soft template method in microemulsion system, followed by grafting of –SH and oxidation of –SH to –SO 3 H at room temperature to avoid use of corrosive sulfonating agents such as concentrated H 2 SO 4 . Dandelion-like porous structures of the SiNF–SO 3 H catalyst provided accessible and abundant catalytic sites ensuring high activity for furfuryl alcohol conversion (100%). Mixed-solvent γ -valerolactone-water (GVL-H 2 O) inhibited undesirable furfuryl alcohol polymerization reactions ensuring highly selective conversion of furfuryl alcohol to levulinic acid. Combination of catalyst and solvent system allowed achievement of the highest levulinic acid yields that have been reported to date. Both the catalyst synthesis protocol and reaction solvent (GVL-H 2 O) are green and sustainable. The SiNF–SO 3 H/(GVL-H 2 O) catalytic system has application to many acid catalyzed schemes for lignocellulosic biomass conversion.
✓ 已验证
产品关联
DOI
高影响因子
SCIENCE OF THE TOTAL ENVIRONMENT
·
2021
·
IF 7.963
Tao Zhou,Yi Han,Wei Xiang,Chen Wang,Xiaohui Wu,Juan Mao,Mingjie Huang
Heterogeneous catalytic activation mechanisms of peroxydisulfate (PDS) by transition metal oxides are generally attributed to the interactions between catalysts and PDS, however, the role of the co-existed organic substrate was largely overlooked in the past studies. In this work, phenol was selected as the target organic pollutant in a CuO/PDS system to evaluate its deep-seated role in participating in the effective activation of PDS. First, optimized reaction conditions as pH of 6.0, CuO of 5.96 g·L −1 and PDS of 2.5 mM were obtained by the response surface methodology (RSM) with a phenol degradation efficiency of 84.0%. It was further found that pre-adsorption of phenol or PDS led to obviously different performances in the phenol degradation with/without the radical scavengers. Two different activation pathways of PDS, i.e., the non-radical pathway mediated by surface deprotonated phenol to generate 1 O 2 and the radical pathway mediated by structural Cu(I)/Cu(II) to produce SO 4 − , were therefore proposed, and the former was predominant in the CuO/PDS/phenol system. In addition, HCO 3 − and HPO 4 2− could strongly inhibit the phenol degradation while Cl − and NO 3 − only performed negligible effects. NaOH washing could regenerate the surface hydroxyl groups and recover the catalytic ability of CuO. The result of this study integrated the interactions among the catalyst, oxidant and substrate, providing new insights into environmental-friendly PDS activation processes.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）