CHEMICAL ENGINEERING JOURNAL
·
2021
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IF 13.273
Ming Lei,Yao Tang,Huimin Wang,Lihua Zhu,Guihua Zhang,Yu Zhou,Heqing Tang
It is still very difficult to achieve rapid cleavage of C-Cl bond of highly-chlorinated benzenes by catalytic reduction process under mild conditions. By using pentachlorobenzene (PentaCB) as a representative of highly-chlorinated benzenes, we proposed a strategy to achieve rapid and complete dechlorination of highly-chlorinated benzenes by exploiting palladium with low content deposited g-C 3 N 4 (Pd/g-C 3 N 4 ) as a catalyst with NaBH 4 as a reductant. Under favorable conditions, this strategy yielded a dechlorination efficiency of 100% for PentaCB (0.4 mmol L −1 ) in methanol solution at 30 °C within 20 min, and especially the consumption of NaBH 4 is as low as 10 mmol L −1 with a molar ratio of Cl atoms to NaBH 4 of only 1:5. A hydro-dechlorination pathway was confirmed to dominate the dechlorination of PentaCB, which involves active hydrogen species (H*) as being identified by electron spin resonance (ESR) monitoring and isotope labelling experiments. The dechlorination rate constant value of chlorobenzenes (CBs) was only a little dependent on the number of chlorine atoms and the chlorine atom with smaller steric hindrance was prior to be substituted by H*. A catalytic mechanism that Pd nanoparticles played an important role on both the weakening/breaking of C-Cl bond and the formation of active hydrogen species was further clarified: Pd exerts affinity interaction on chlorine atoms at ortho -position of CBs molecules to form adsorbed state [CBs] ads ; H* was formed on the Pd surface due to its strong ability in H* retainment; subsequently the generated H* attacks the C-Cl bond in [CBs] ads to achieve hydrodechlorination. The new method provides a highly efficient method to remove halogenated pollutants.
研究领域:
环境科学
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催化化学
✓ 已验证
DOI
高影响因子
RARE METALS
·
2024
·
IF 9.6
Hu Xiao-Jie,Sun Yu-Han,Liu Ling-Yue,Mao Dan-Jun,Zheng Shou-Rong
Monochloroacetic acid (MCAA) is identified as a highly carcinogenic disinfection by-product in chlorinated drinking water. In this study, a series of CeO 2 -supported Pd catalysts (Pd/MCeO 2 ) were synthesized through one-step calcination of Pd-loaded Ce-UiO-66-BDC (Ce-MOF), and the liquid-phase catalytic hydrodechlorination of MCAA was explored using these catalysts. For comparison, Pd/CeO 2 catalysts were additionally synthesized using the conventional impregnation method. The characterization results reveal that the catalysts exhibit strong metal–support interaction, leading to high Pd dispersion and Pd n + content. Additionally, the calcination temperature significantly influences catalytic performance, with the catalyst calcined at 500 °C (Pd/MCeO 2 -500) demonstrating the highest catalytic activity and achieving complete dechlorination of MCAA within 50 min. Furthermore, it is found that the catalytic MCAA hydrodechlorination using the catalysts adheres to the Langmuir–Hinshelwood model. Accordingly, low reaction pH is favorable for the catalytic hydrodechlorination of MCAA, enhancing MCAA adsorption on the catalyst surface due to the electrostatic interaction between MCAA and the catalyst surface. Theoretical results suggest that the presence of Pd n + efficiently facilitates MCAA adsorption and C–Cl cleavage, thus significantly enhancing the liquid-phase catalytic hydrodechlorination. Graphical abstract
研究领域:
环境科学
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催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Yinan Liu,Xiangyi Tang,Fei Shen,Jiahong Zou,Yanjun Yin,Zhaojie Jiao,Xiaoshu Lv,Wenyang Fu,Yan Zou,Guangming Jiang,Hong Liu
Electrocatalytic hydrodehalogenation (ECHD) offers a promising approach for detoxification of the halogenated antibiotics via hydrogenolysis of the C-X bonds (X = F, Cl or Br). Herein we demonstrated that the commercially-available cobalt phthalocyanine (CoPc) molecules with a high-loading of −[Co-N 4 ]- moieties (Co wt%: 10.8 %) were exceptionally active for hydrogenolysis of the C-Cl bonds in florfenicol (FLO). It afforded an impressive mass activity of 6.2 g FLO h −1 g -1 Co , a low Co leaching of 0.34 μg/L and a strong tolerance to interference from impurities in water, significantly surpassing reported Co/Fe/Ni-based particle and single-site counterparts. Mechanistic studies revealed that the ECHD on CoPc underwent a direct electron transfer manner rather than the atomic hydrogen (H*)-mediated indirect way, and the ECHD efficacy was affected by both the electron and proton transfer kinetics. The single-atom Co, with its d orbitals constituting the lowest unoccupied molecular orbitals of CoPc, served as the primary active site. It facilitated both electron and proton transfer, as well as the cleavage of the C-Cl bond but not the C-F bond. In a continuous-flow cell, the CoPc/C-driven ECHD reduced the antibacterial activity of a FLO-contaminated natural lake water sample by 90.8 % with an energy consumption of 0.19 kwh g -1 FLO . This study highlighted great promise of the single-atom metal-bearing molecular catalyst toward the sustainable detoxification of halogenated antibiotics-contaminated water.
研究领域:
环境科学
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催化化学
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抗生素污染治理
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF VINYL & ADDITIVE TECHNOLOGY
·
2023
·Vol. 29
·期 2
·410-423
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IF 2.7
Guifang Du,Zhaogang Liu,Peijie Jia,Jinsheng Duan,Ruifeng Ma,Yonggang Liu,Fushan Feng,Yanhong Hu,Jinxiu Wu
In this research, ZnAlLa-itaconate-LDHs was synthesized by means of Co-precipitation-hydrothermal method. The effects of aluminum-lanthanum ratio, co-precipitation time, hydrothermal time, and hydrothermal temperature on the crystal structure were studied. As a result, the optimum condition was found to be: n(Al 3+ ): n(La 3+ ) = 10:1, co-precipitation time 24 h, hydrothermal time 8 h, and hydrothermal temperature 180°C. The influence of ZnAlLa-itaconate-LDHs on the thermal stability properties and plasticizing properties of PVC were investigated, exhibiting long-term stability of 76 min with short plasticizing time of 1.11 min. Long-term thermal stability mechanism was studied by FTIR before and after hydrochloric acid treatment. It was demonstrated that the thermal stabilizer ZnAlLa-itaconate-LDHs prevented the rupture of the C Cl bond in PVC and inhibited the development of HCl. Consequently, impeded the production of CC bond and playing a role in thermal stabilization of PVC.
研究领域:
材料科学
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高分子化学
✓ 已验证
产品关联
DOI
高影响因子
ACS ES&T Engineering
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2025
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IF 6.7
Hehe Qian,Tinghui Ma,Lili Shi,Shu Yan,Haisong Cui,Xueqing Luo,Fang Chen,Yuetan Su,Zhongbiao Wu,Xiaole Weng
Electrocatalytic hydrodechlorination (EHDC) is a promising strategy for remediating chlorinated organic pollutants by utilizing reactive hydrogen (H*) to cleave C–Cl bonds. Addressing the challenge of simultaneously optimizing H* generation and targeted pollutant adsorption/activation, this work introduces synergistic surface engineering of RuPd alloy nanocatalysts. Compositionally controlled RuPd nanoparticles (RuPd2, Ru2Pd3, and Ru2Pd) were synthesized via seed-mediated growth, yielding uniform sub-3.5 nm nanoparticles with homogeneous elemental distribution. The optimal RuPd2 electrocatalysts achieved 97.1% 2-chlorophenol conversion within 6 h at −0.85 V vs Ag/AgCl, exhibiting a mass activity of 28.3 min–1 g–1Pd, representing a 5.6-fold enhancement over monometallic Pd. Moreover, RuPd2 demonstrated enhanced durability, maintaining performance with less than 5% efficiency loss over 10 cycles. This enhanced EHDC performance originated from dual synergistic effects. Electron transfer from Ru to Pd facilitated H* generation kinetics, evidenced by a near-optimal ΔGH* (−0.25 eV) at Pd–Pd–Pd hollow sites, while Ru-rich surface domains significantly strengthened 2-chlorophenol adsorption and elongated the C–Cl bond to facilitate dechlorination. These spatially separated synergistic sites collectively achieve higher EHDC efficiency, establishing a unified catalyst design strategy that effectively orchestrates coupled surface processes, and provides a significant advance for efficient EHDC technology with broad environmental remediation implications.
研究领域:
环境催化
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纳米材料化学
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污染物降解
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电化学
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表面科学
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能源与环境工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Yuqi Zhang,Jiasi Yan,Rixin You,Meng He,Ligen Wang,Minghui Liang
The catalytic epichlorohydrin (ECH) hydrogenation to chloro-propanol is of great industrial importance due to the extensive application of chloro-propanol as an intermediate for pharmaceutics, fine chemicals, and polymers. The challenge of this catalytic reaction lies in that dechlorination can hardly be inhibited in the selective hydrogenation of the epoxy group because the bond energy of the C-Cl bond is very close to that of the C O bond. Herein, we demonstrated that the selectivity of chloro-propanol could be improved from 82.2 % to 94.6 % by incorporating a small amount of Cu single atoms into Pt/C catalysts to inhibit dechlorination. More interestingly, the ring-opening site of the epoxy group can be also engineered by the incorporation of Cu single atoms, as evidenced by the significant increase in the selectivity of 3-chloro-1-propanol from 0.2 % to 14.5 %. Comprehensive characterizations and density functional theory (DFT) calculations were carried out to understand the interplay of Cu single atoms and Pt nanoparticles as well as its effect on the catalytic performance. The insights gained in this study will benefit the development of catalysts, especially the bimetallic catalysts for the selective hydrogenation of halogeno-aliphatic compounds.
研究领域:
催化
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化学工程
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材料科学
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Guoshuai Liu,Shanshan He,Hua Zou,Shijie You
Electrocatalytic hydrodechlorination (EHDC) is a promising approach for decomposing chlorinated organic compounds in water treatment. However, the efficiency of EHDC is constrained by kinetic mismatch between C−Cl bond cleavage and atomic hydrogen (H*) utilization. Herein, we develop a heterostructured Pd-H x WO 3 electrocatalyst with Pd nanoparticles (Pd NPs) anchored on H x WO 3 substrate, which can efficiently decompose 2,4-dichlorophenol (2,4-DCP) by taking advantage of the hydrogen spillover effect. Specifically, the resulting Pd-H x WO 3 electrocatalyst exhibits superior dechlorination rate constant ( k = 1.142 h −1 ) and Faradic efficiency (FE = 10.1 %) than monometallic Pd ( k = 0.3600 h −1 , FE = 3.74 %) and bare H x WO 3 ( k = 0.1167 h −1 , FE = 2.11 %), along with exceptional pH adaptability and stability. Electron spin resonance (ESR) and electrochemical and kinetic isotope effect (KIE) measurements indicate that the transport of the H* from H x WO 3 to Pd NPs is the key to enhanced EHDC performance. Theoretical studies reveal that the Volmer step of water dissociation to produce H* is more favorable due to lower transition state (TS) energy (0.344 eV) on H x WO 3 than that on Pd (TS = 0.532 eV). Furthermore, the interfacial electron redistribution in Pd-H x WO 3 lowers the thermodynamic (Δ G = 0.207 eV) and kinetic (Δ G = 0.239 eV) barriers for H* transfer from the internal site of H x WO 3 to interfacial Pd sites, thereby facilitating the proton-coupled electron transfer (PCET)-mediated EHDC on Pd site. This work provides a new proof-in-concept demonstration for designing hydrogen spillover-integrated electrocatalysts to enhance H* generation-transfer-utilization in EHDC for water decontamination.
研究领域:
环境化学
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电催化
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水净化
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材料科学
·
可持续化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）