SYNTHESIS-STUTTGART
·
2022
·Vol. 54
·期 09
·2258-2266
·
IF 2.969
Bao Gao,Xiaojun Liu,Qian Yan,Ruiting Yang,Tao Jiang,Xiuli Zhang
A novel and convenient method for the highly chemoselective synthesis of β-hydroxysulfides mediated by DMSO is reported. This eco-friendly reaction was amenable to a broad range of substrates and provided the desired β-hydroxysulfides in moderate to good yields with high selectivity via radical process. Moreover, several pharmaceutical and bioactive molecules were also suitable substrates for this reaction conditions to afford the targeted products in good yields.
研究领域:
有机化学
·
药物化学
✓ 已验证
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2023
·
IF 13.6
Haoyu Luo,Yi Wan,Jie Li,Yuhao Cai,Zhi Dang,Hua Yin
In wastewater treatment by persulfate-based advanced oxidation processes (PS-AOPs), electron-deficient aromatic pollutants (EDAPs) are refractory to nonradical pathway. To explore an efficient degradation pathway for EDAPs, Mg x Cu-biochar (BC) (x = 0.5, 1, 1.5) activated peroxydisulfate (PDS) was developed, which could trigger reductive species (•H) to reduce EDAPs first, and subsequently facilitate electron-transfer degradation of reduced intermediates. The roles of Mg-doping in Mg x Cu-BC to promote PDS activation and 2,4-dibromophenol (DBP) degradation were investigated. The mechanisms were then explored via electron paramagnetic resonance (EPR), chemical probes and Density Functional Theory (DFT) calculations. The results showed that Mg-doping improved metal-support interactions (MSIs) of Mg x Cu-BC, inducing •H formation via electron transfer from Cu atoms during PDS activation, which was thermodynamically favorable. The degradation rate of DBP ( k obs , 0.0494 min –1 ) and Br – release (5.35 mg L –1 ) in Mg 1 Cu-BC systems were more 31 and 33 times than that in Cu-BC/PDS system, respectively. The degradation mechanism of •H-enhanced electron transfer processes was that •H attacked one Br group of DBP, and then debrominated intermediates were mineralized by electron transfer processes in the Mg 1 Cu-BC/PDS system. Overall, this study reports a novel pathway in PS-AOPs for selective degradation of EDAPs in wastewaters.
研究领域:
环境科学
·
废水处理
·
高级氧化工艺
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2022
·
IF 9.794
Dazhong Zhong,Dong Wang,Tan Li,Lu Hao,Zizai Ma,Tao Zhao,Genyan Hao,Xiaoguang Wang,Guang Liu,Jinping Li,Qiang Zhao
NiFe-layered double hydroxide (NiFe–OH) is one of the most promising candidate materials for the oxygen evolution reaction (OER) in an alkaline electrolyte . However, it is difficult to be oxidized into Ni 3+ FeOOH active species with high valence Ni under mild conditions; thus, the activity under mild conditions is inferior. We report here that NiFe–OH is converted to amorphous NiFeO x H y (a3-NiFe-OH) with easily oxidized electron-deficient Ni 2+ after pre-oxidation in an alkaline solution boosts the OER performance under mild conditions. The amorphous structure of a3-NiFe-OH also enlarges the electrochemically active area to expose more active sites. It merely needs an overpotential of 350 mV at 10 mA cm −2 in 0.1 M KHCO 3 electrolyte. The corresponding Tafel slope is as low as 89 mV dec −1 . This work affords a strategy for developing (near) neutral OER catalysts.
研究领域:
电化学
·
材料科学
·
催化
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2020
·
IF 9.038
Shi-Wen Lv,Jing-Min Liu,Ning Zhao,Chun-Yang Li,Zhi-Hao Wang,Shuo Wang
Nowadays, designing highly active photocatalysts for pollutant degradation under visible light still remains a challenging problem. Herein, a novel benzothiadiazole functionalized Co-doped MOF-based photocatalyst with electron deficient unit was first synthesized via a feasible step-by-step assembly strategy. Benzothiadiazole, as typical electron deficient group, could effectively promote the separation and transfer of photoinduced charge carriers. The implantation of Co ion could be served as an effective mediator to further facilitate the charge transfer through a Co 3+ /Co 2+ redox pathway. Interestingly, the as-synthesized Co-MIL-53-NH-BT exhibited significantly enhanced photocatalytic degradation capacity for BPA and OFX under visible light irradiation, with removal efficiency as high as 99.9 % and 99.8 % within 120 min. TOC analysis suggested that majority of contaminants had been degraded into CO 2 and H 2 O. The important parameters influencing the photocatalytic activity were investigated, and the kinetics study was also conducted. The possible degradation pathways and the possible photocatalytic mechanism were proposed. More importantly, the as-synthesized Co-MIL-53-NH-BT showed good reusability, stability as well as universal applicability. To sum up, current work not only developed an efficient and visible-light active photocatalyst for treating organic-contaminated wastewater, but also afforded some novel insight into the utilization of benzothiadiazole in MOF-based photocatalyst towards improving photocatalytic activity.
研究领域:
环境科学
·
材料科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ChemPlusChem
·
2020
·Vol. 85
·期 3
·503-509
·
IF 2.753
Meng-Yao Chao,Jing Chen,Xiao-Yu Wu,Rui-Yao Wang,Pei-Pei Wang,Lifeng Ding,David J. Young,Wen-Hua Zhang
Graphical Flexible friend : A metal–organic framework sustained by a Cd 5 cluster shows flexible behavior and coordination preference toward electron-deficient rather than electron-rich pyridyl ligands. Density functional theory calculations offer binding energies of the electron-deficient 4-pyridinealdehyde (1.09 eV) and 4-acetylpyridine (1.36 eV) to the flanking Cd centers, and are larger than those of the electron-rich ligands, such as 4-iodopyridine (0.32 eV) and 4,4′-bipyridine (0.61 eV). A cationic three-dimensional (3D) metal-organic framework (MOF) sustained by an N , N ′-diethylformamide (DEF)-solvated zigzag-shaped Cd 5 cluster secondary building unit (SBU), [Et 2 NH 2 ] 2 [Cd 5 (BTB) 4 (DEF) 2 ] ⋅ 4.75DEF ( 1 a , H 3 BTB=benzene-1,3,5-tribenzoic acid) shows flexible framework behavior and undergoes solvate exchange with CHCl 3 to yield [Et 2 NH 2 ] 2 [Cd 5 (BTB) 4 (DEF) 2 ] ⋅ x CHCl 3 ( 1 b ) accompanied by changes to pore sizes and shapes. Unexpectedly, the DEF solvates coordinated to the central Cd 2+ could not be replaced by strongly donor pyridyl and dipyridyl ligands. Additionally, more electron-deficient pyridyls preferentially coordinated to the flanking Cd 2+ of the Cd 5 SBU, as exemplified by [Et 2 NH 2 ] 2 [Cd 5 (BTB) 4 (DEF) 2 (PyCHO) 2 ] ⋅ x Sol ( 2 a , PyCHO=4-pyridinealdehyde) and [Et 2 NH 2 ] 2 [Cd 5 (BTB) 4 (DEF) 2 (PyAc) 2 ] ⋅ x Sol ( 2 b , PyAc=4-acetylpyridine). Density functional theory (DFT) calculations were used to understand these counterintuitive observations.
研究领域:
材料科学
·
无机化学
·
理论化学
✓ 已验证
DOI
高影响因子
RARE METALS
·
2025
·
IF 11
Wang Zhenxiao,Ning Shuguang,Liu Xiang,Zhao Hongyao,Zhang Wanyu,Cao Liying,Wang Yanyun,Shang Danhong,Zhai Linzhi,Yang Tongyi,Zeng Feng,Zhang Yangping,Yang Fu
The advanced oxidation process presents a perfect solution for eliminating organic pollutants in water resources, and the local microenvironment and surface state of metal reactive sites are crucial for the selective activation of peroxomonosulfate (PMS), which possibly determines the degradation pathways of organic contaminants. In this study, by virtue of the precursor alternation, we constructed the state-switched dual metal species with the porous carbon fibers through the electrospinning strategy. Impressively, the optimal catalyst, featuring the electron-deficient cobalt surface oxidative state and most abundant oxygen vacancies (Ov) with MnO 2 within porous carbon fibers, provides abundant mesoporosity, facilitating the diffusion and accommodation of big carbamazepine molecules during the reaction process. Benefiting from the tandem configuration of carbon fiber-encapsulated nanocrystalline species, a p–n heterojunction configuration evidenced by Mott–Schottky analysis induced local built-in electric field (BIEF) between electron-deficient cobalt and Ov-rich MnO 2 within carbon matrix-mediated interfacial interactions, which optimizes the adsorption and activation of PMS and intermediates, increases the concentration of reactive radicals around the active site, and significantly enhances the degradation performance. As a result, the optimal catalyst could achieve 100% degradation of 20 ppm carbamazepine (CBZ) within only 4 min with a rate constant of 1.099 min −1 , showcasing a low activation energy (50 kJ mol −1 ), obviously outperforming the other counterparts. We further demonstrated the generation pathways of active species by activation of PMS mainly including sulfate radical (·SO 4 − ), hydroxyl radical (·OH), superoxide radicals (·O 2 − ), and singlet oxygen ( 1 O 2 ), unveiling their contribution to CBZ degradation. The degradation route of CBZ and toxicity analysis of various intermediates were further evaluated. By anchoring the optimal catalyst onto polyester fiber sponge, the photothermal conversion synergistic monolith floatable catalyst and its easy recovery can be achieved, showing good reproducibility and generalizability in the practical application. Graphical abstract
研究领域:
环境科学
·
材料科学
·
化学工程
·
纳米技术
·
水处理
✓ 已验证
产品关联
DOI
高影响因子
DYES AND PIGMENTS
·
2020
·
IF 4.613
Wei Ma,Yue Wang,Jing Gao,Ru Sun,Jian-Feng Ge
A series of bispyrazolopyridine (BPP) dyes with electron deficient or electron rich aromatic rings were synthesized, and their optical properties were evaluated. Dyes 3a-c connect the BPP unite with electron deficient moieties (pyridine ( 3a ), nitrobenzene ( 3b ), benzonitrile ( 3c )) by a single bond; dyes 3d-e consist of BPP and electron rich moieties (anisole ( 3d ), N,N -diethylaniline ( 3e )). Their optical properties in five organic solvents and water solution were investigated. They show absorption at 310–375 nm and emission at 400–580 nm in organic solvents. Meanwhile, dyes 3a and 3c-d have high fluorescence quantum yield in organic solvents (40%–84%) and aqueous solution (69%–89%), and they also exhibit excellent light stability. The pH-influenced optical properties tests indicate dyes 3a-e show different fluorescence intensities from alkaline (pH = 10.0) to acid condition (pH = 1.0). The protonation of BPP units and aromatic rings was used to explain their emission property, while (TD)DFT calculations were developed to understand the differences in the optical properties.
研究领域:
化学
·
材料科学
·
光学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2021
·
IF 8.128
Qingxiang Xu,Long Zhao,Yuhan Ma,Rui Yuan,Maosong Liu,Zhaoli Xue,Henan Li,Jianming Zhang,Xinping Qiu
Charge states at the catalytic interface can intensely alter the charge transfer mechanism and thus the oxygen reduction performance. Two symmetric cobalt porphyrins with electron deficient 2,1,3-benzothiadiazole (BTD) and electron-donating propeller-like triphenylamine (TPA) derivatives have been designed firstly, to rationally generate intramolecular partial charges, and secondly, to utilize the more exposed molecular orbitals on TPA for enhancing the charge transfer kinetics. The catalytic performance of the two electrocatalysts was examined for oxygen reduction reactions (ORR) in acidic electrolyte. It was found that BCP1/C with two BTD groups showed greater reduction potential but less limiting current density as compared to BCP2/C bearing BTD-TPA units. The reduced potential of BCP2/C was proposed to the introduction of the electron-donating ability of TPA, which may decrease the adsorption affinity of oxygen to the cobalt center. Both dipole-induced partial charge effect and the more exposed cation orbitals of the 3D structural TPA were proposed to contribute to the increased response current of BCP2/C . In addition, BCP2/C attained more than 80% of H 2 O 2 generation in acidic solution, which may also relate to the structural effect. These findings may provide new insight into the structural design of organic electrocatalysts and deep understanding on the interfacial charge transfer mechanism for ORR.
研究领域:
电化学
·
催化
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Ze-Min Zhao,Yu Zhang,Yu Chen,Jieying Jing,Wen-Ying Li
Nickel–aluminum (Ni–Al) spinel catalysts with distinct Ni/Al molar ratios were synthesized to construct Ni 2+ coordination sites. Owing to the favorable distribution of Ni 2+ coordination sites and the presence of suitable concentration of Ni 2+ in octahedral sites, Ni/Al-0.725 catalyst achieved an 86.1 % average yield of perhydrophenanthrene, which was higher than that obtained with Ni/Al-0.25 (6.3 %). Characterization results indicated that Ni 2+ of the Ni/Al-0.725 catalyst was present in octahedral sites and ∼ 40.4 % Ni 2+ was reduced to Ni, whereas the active Ni metal of Ni/Al-0.25 catalyst mainly comprised Ni 2+ occupying tetrahedral sites as precursors. Furthermore, the Ni/Al-0.725 catalyst exhibited the smallest Ni particle size (2.82 nm) and the largest Ni available surface (19.62 m 2 /g sample ), which helped alleviate competitive adsorption among aromatic hydrocarbons. The Ni reduced by the spinel catalysts was in an electron-deficient state, which enhanced the adsorption of polycyclic aromatic hydrocarbons.
研究领域:
催化
·
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Haiyang Xie,Dan Tang,Yanjuan Zhang,Zuqiang Huang,Huayu Hu,Qian He,Hongbing Ji,Tao Gan
The design of non-noble metal single-atom catalysts (SACs) with superior performance for semi-hydrogenation of alkynol to alkenol is remarkable but challenging. Herein, fluorine-tuned Fe SACs supported on N, F-codoped carbon (Fe 1 -NFC) with a Fe-N 4 F 1 structure is successfully prepared via a complexation method. The axial F-doping can modulate the electronic structure of the metalloporphyrin-like active sites (Fe-N 4 ), promoting the transfer of electrons from Fe atoms to F atoms to form electron-deficient Fe δ+ species. As a result, the Fe 1 -NFC catalyst shows a remarkable activity for the semi-hydrogenation of 2-methyl-3-butyn-2-ol to 2-methyl-3-buten-2-ol under mild conditions, with a TOF of 9163 h −1 and a selectivity of 96 % at 97 % conversion, both much higher than that of the Fe SACs supported on N-doped carbon (Fe 1 -NC). Density functional theory (DFT) calculations reveal that the excellent catalytic activity is attributed to the interfacial electronic effect of Fe species induced by axial F-doping, thereby enhancing the exothermic adsorption of alkynol on the Fe-N 4 F 1 structures and accelerating the desorption of alkenol to against the overhydrogenation.
研究领域:
催化
·
材料科学
·
化学工程
·
理论化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）