ChemCatChem
·
2021
·Vol. 13
·期 21
·4610-4617
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IF 5.686
Yifei Yang,Linsen Zhou,Jun Chen,Ruizhi Qiu,Yunxi Yao
Graphical Highly dispersed Pt clusters supported on TiN substrates favor the formation of highly reactive dual sites. Molecular O 2 dissociatively adsorbs on the Ti−Ti bridge sites to form titanium oxynitride (TiN x O y ) skin and the oxygen atom binding on Ti sites readily react with the adjacent CO adsorbed on Pt to attain the catalytic cycle. The interfacial synergistic effect between Pt and TiN results in superior performance in the low-temperature CO oxidation. The metal-support interfacial synergistic catalysis allows the competitive reaction steps to occur in close proximity at different sites, thus decreasing the activation barrier and improving the catalytic efficiency. Combining the structural characterization, reactivity assessments and density functional theory (DFT) calculations, it is found that highly dispersed Pt clusters on TiN substrates favor the formation of Pt−TiN interfacial dual sites, which are highly reactive for the low-temperature CO oxidation with an apparent activation energy as low as 38.7 kJ mol −1 , much less than that on the traditional Pt/TiO 2 or Pt/SiO 2 catalysts. At low temperature, the surface sites of Pt are saturated with CO adsorption due to its high adsorption energy and the molecular O 2 dissociatively adsorbs on the Ti sites to form the titanium oxynitride (TiN x O y ) skin with a low barrier of 0.1 eV. The O atoms binding on Ti sites readily react with the adjacent CO molecules adsorbed on the perimeter of Pt clusters to attain a catalytic cycle with a reaction barrier of 0.5 eV. The interfacial synergistic effect between Pt and TiN is the origin of the low temperature CO oxidation activity on the metal-nitride catalysts.
研究领域:
催化
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材料科学
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化学工程
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表面化学
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2021
·
IF 5.816
Wei Lai,Lihong Ge,Huaming Li,Yilin Deng,Bin Xu,Bo Ouyang,Erjun Kan
The electrochemical water splitting to produce H 2 in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry + ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH) 2 heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH) 2 heterostructure during the first 30 min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH) 2 amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH) 2 interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30 mV at a H 2 -evolving current density of 10 mA/cm 2 and 153 mV at 100 mA/cm 2 , as well as a small Tafel slope of 46.8 mV/dec in 1 M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24 h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH) 2 heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH) 2 interface reducing the energy barrier of H∗ adsorption thus promoting the HER performance.
研究领域:
电化学
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催化
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材料科学
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光谱学
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高影响因子
Journal of Water Process Engineering
·
2026
·
IF 6.6
Guangyu Duan,Xiaoya Li,Shuai Wang,Ru Zheng
The PNVP-GO composite was fabricated for efficient heavy metal removal. • The composite exhibited a high adsorption capacity of 86.96 mg·g −1 for Pb 2+ . • Topological analyses unveiled a synergistic dual-site specific adsorption mechanism. • Flexible PNVP chains overcome Pb 2+ lone pair hindrance via V-shaped cavity formation. A poly( N -vinylpyrrolidone)-graphene oxide (PNVP-GO) composite synthesized via optimized suspension polymerization demonstrated exceptional performance in removing Cu 2+ , Ni 2+ , and Pb 2+ . Adsorption of Cu 2+ and Ni 2+ followed the Langmuir isotherm, Pb 2+ recognition exhibited pronounced surface energetic heterogeneity accurately described by the three-parameter Sips and Toth models. Mechanistically, all uptake processes were rate-governed by spontaneous, endothermic chemisorption, consistent with the pseudo-second-order (PSO) kinetics, achieving maximum capacities of 73.96, 77.76, and 86.96 mg·g −1 for Cu 2+ , Ni 2+ , and Pb 2+ , respectively. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) confirmed chemisorption, while density functional theory (DFT) coupled with wavefunction topological analyses (ELF and IGMH) unveiled distinct dual-site specific adsorption mechanisms. Rigid GO carboxyl domains efficiently coordinate Cu 2+ and Ni 2+ but experience steric repulsion against the stereochemically active 6s 2 lone pair of Pb 2+ . Crucially, flexible PNVP chains overcome this barrier via conformational torsion (forming a V-shaped cavity) to accommodate the massive lone pair. A life cycle assessment (LCA) evaluated environmental sustainability and identified grid electricity for vacuum freeze-drying as the primary driver of Global Warming Potential (GWP, 75%). In comparison, ethanol washing was identified as the major contributor to Marine Eutrophication Potential (MEP, 29%). This study provides a universal theoretical paradigm for designing heavy metal adsorbents and highlights eco-design pathways to mitigate their life-cycle environmental footprints. Download: Download high-res image (288KB) Download: Download full-size image
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Journal of Materials Chemistry A
·
2025
·
IF 9.5
Songru Xie,Longbo Jiang,Wei Liu,Qiaomei Lu,Guanjun Zeng,Hou Wang,Jiajia Wang,Xingzhong Yuan,Haoyun Chen,Haiwei Jiang
Carbon quantum dots (CQDs) have gained extensive application in advanced oxidation processes (AOPs) due to the advantages of their unique carbon network structure. However, CQDs still face issues such as uneven electron distribution and low utilization of active sites during application, which have limited their further use in peroxymonosulfate (PMS)-based AOPs. In this study, ferrous gluconate derived iron-doped CQDs (Fe-CQDs) with a unique structure of Fe doping sites were synthesized by a one-step method to activate PMS. The degradation of ciprofloxacin in the Fe-CQDs/PMS system reached 98.19% within 30 minutes, surpassing that in the CQDs/PMS system (30.39%) and PMS system (25.30%), with approximately 10.74 times and 12.92 times higher reaction rates, respectively. Mechanistic studies have revealed that the Fe3+ sites on Fe-CQDs can optimize the electronic structure of CQDs and enhance the utilization of active sites within the carbon network structure, improving the electron transfer ability from Fe-CQDs to PMS. This optimization strengthens the contact and activation of PMS by Fe-CQDs through the network capture effect. Simultaneously, the carbon network on Fe-CQDs provides abundant reactive sites for PMS activation and pollutant degradation reactions. DFT calculations were utilized to explore the correlation between pollutants and active species by computing their corresponding Fukui functions. This work presents novel insights into the network capture effect on the Fe-CQD-based PMS activation system.
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高影响因子
FUEL
·
2022
·
IF 8.035
Xu Pan,Fei Li,Ye Chen,Qing Wen,Xiaoqian Li,Junhong Wang,Haitao Xu,Liuqingying Yang
As a green conversion/energy storage device, the practical application of microbial fuel cell (MFC) was limited with its low power generation. The extracellular electron transfer efficiency was one of the key factors affecting the power generation performance of MFC. This paper reported the carbonized derivative Co-Ni-ZIF@NC derived from PANI-doped Co-Ni-ZIF with conductivity, biocompatibility and high electrocatalytic activity. Density functional theory (DFT) confirmed the strong interaction between the electrode surface and microorganisms. The maximum power density of the MFC with Co-Ni-ZIF@NC anode (8.67 W/m 3 ) was 1.47 time higher than that of Co-Ni-ZIF@C-800 (5.96 W/m 3 ). High-throughput sequencing revealed that Co-Ni-ZIF@NC catalyst facilitated the screening of relevant functional microbial communities in microbial membranes, leading to the reinforcement of power generation in MFC. PICRUSt predicted the relative abundance of functional genes, confirmed the spontaneous enrichment behaviour of functional microorganisms to the electrode surface, and identified cytochrome c552 as the dominant role in the EET process. The above foregoing mainly due to the doping of PANI, improved the content of pyrrolic N on the surface of derivatives, protected the original crystal morphology, promoted the approaching behaviour of conductive flagella to the anode surface and shortened the electron transport distance, thus Co-Ni-ZIF@NC exhibited superb bioelectrocatalytic activity.
研究领域:
能源材料
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电化学
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微生物电化学系统
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计算化学
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环境生物技术
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高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2023
·
IF 13.6
Jiahao Lai,Peng Xiao,Yafei Li,Shihai Cui,Jing Yang,Hongzhen Lian
Broadening the light absorption and inhibiting carrier's recombination are vital to the improvement of photocatalytic performance. Herein, self-assembly 3D hierarchical microsphere BiOIO 3 /Bi 5 O 7 I Z-scheme heterojunction with carrier transfer channel was firstly fabricated by in-situ solvothermal method. The degradation efficiency for bisphenol A (BPA) reached 98.9 % within 60 min visible light irradiation. The enhanced photocatalytic activity was benefited from the Z-scheme system assisted by iodate/iodide (IO 3 - /I - ) as carrier transfer channel that not only accelerated the interfacial charge separation, but also provided massive reactive centers for obtaining high redox capacity. The vulnerable sites and the degradation pathways of BPA were identified by density functional theory calculations and liquid chromatography-mass spectrometry analyses. The toxicity of BPA and its intermediates were predicted by ECOlogical Structure Activity Relationship (ECOSAR) and the results demonstrated that BPA was eventually mineralized to harmless products. The Z-scheme charge transfer mechanism was deeply elucidated based on the role of active species (·O 2 - , ·OH and h + ), band structure and carrier separation efficiency. This study provides a promising strategy for the photoactivity enhancement of bismuth based heterojunction in environment purification.
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高影响因子
Advanced Science
·
2021
·Vol. 9
·期 2
·2102530
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IF 16.806
Fazal Raziq,Amil Aligayev,Huahai Shen,Sharafat Ali,Rahim Shah,Sajjad Ali,Syedul H. Bakhtiar,Asad Ali,Naghat Zarshad,Amir Zada,Xiang Xia,Xiaotao Zu,Muslim Khan,Xiaoqiang Wu,Qingquan Kong,Chunming Liu,Liang Qiao
Artificial Z-scheme, a tandem structure with two-step excitation process, has gained significant attention in energy production and environmental remediation. By effectively connecting and matching the band-gaps of two different photosystems, it is significant to utilize more photons for excellent photoactivity. Herein, a novel one-photon (same energy-two-photon) Z-scheme system is constructed between rGO modified boron-nitrogen co-doped-WO 3 , and coupled CdSe quantum dots-(QDs). The coctalyst-0.5%Rh x Cr 2 O 3 (0.5RCr) modified amount-optimized sample 6%CdSe/1%rGO3%BN-WO 3 revealed an unprecedented visible-light driven overall-water-splitting to produce ≈51 µmol h −1 g −1 H 2 and 25.5 µmol h −1 g −1 O 2 , and it remained unchanged for 5 runs in 30 h. This superior performance is ascribed to the one-photon Z-scheme, which simultaneously stimulates a two photocatalysts system, and enhanced charge separation as revealed by various spectroscopy techniques. The density-functional theory is further utilized to understand the origin of this performance enhancement. This work provides a feasible strategy for constructing an efficient one-photon Z-scheme for practical applications.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Chenxi Li,Yadan Guo,Dandan Tang,Yaoping Guo,Guanghui Wang,Hao Jiang,Jun Li
The density functional theory (DFT) not only is indispensable to calculate the electronic structure and chemical property of photocatalysts, but also provides guidance to the understanding of the mechanisms involved in photocatalysis. Herein, a novel Zn doped AgFeO 2 was successfully constructed for enhancement of Cr(VI) reduction and azophloxine decomposition under visible light irradiation. The DFT calculation was employed to set up a Zn doped AgFeO 2 model to simulate its split Zn 3 d levels shift to lower energy to optimize the band structure. With Zn doped, the AgFeO 2 exhibit enhanced reducing capacity. As expected, compared to unmodified AgFeO 2 , Zn doped AgFeO 2 can reduce and remove more than 90% of Cr(VI). Based on theoretical analysis and systematic experiments, the enhanced photocatalytic of Zn doped AgFeO 2 were arisen from superoxide radical (O 2 − ) generation and photocarrier transfer via oxygen vacancies (OVs) enrichment, and the OVs would provide coordinatively unsaturated sites for Cr(VI) adsorption. We expect this work can provide new insights into the photocatalytic utilization of AgFeO 2 .
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CHEMICAL ENGINEERING JOURNAL
·
2019
·
IF 8.355
Hanzi Liu,Changfu You,Haiming Wang
Transient in-situ IR spectroscopy was performed to analyze the molecular behavior of selective catalytic reduction of NO with NH 3 on V 2 O 5 -WO 3 /TiO 2 catalyst. During NH 3 adsorption, an unexpected growth in the intensity of Lewis acid sites was observed due to the hydrogen migration, which was verified by the DFT calculation and the existence of intermediate species. The comparison between the isolated atmosphere experiments and the simultaneous exposure of NH 3 -NO-O 2 on catalytic monolayer demonstrated that: (i) there exists a pathway for Lewis to Brønsted acid sites transformation at T > 300 °C, (ii) the rate determining step of the SCR cycle involves in the re-oxidation of acid sites by O 2 at 200–300 °C. Generally, the Lewis acids are crucial at high temperatures, while Brønsted acids dominate the overall reaction at lower temperatures. Based on the experimental data and the DFT calculation, a mechanism for ammonia adsorption, acidity conversion and re-oxidation for the redox loop of the de-NOx reaction was proposed. The findings shed light on the understanding of relative strength of NO reduction and acid re-oxidation at different temperatures.
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ChemSusChem
·
2023
·Vol. 16
·期 9
·e202300154
·
IF 8.4
Yuheng Lin,Deshuai Yang,Chaoyu Meng,Chunying Si,Quanxing Zhang,Guixiang Zeng,Wei Jiang
Graphical Replace the atom : Ni 2+ -doped MgO catalyst is developed via a combined theoretical and experimental approach, which exhibits excellent performance toward the glycolysis of polyethylene terephthalate (PET) with a bis(hydroxyethyl) terephthalate yield of 93.7 %. Ni 2+ doping is found critical to the generation of O − and deprotonated ethylene glycol which break the PET chain via nucleophilic attack. Developing efficient and eco-friendly catalysts for selective degradation of waste polyethylene terephthalate (PET) is critical to the circular economy of plastics. Herein, we report the first monatomic oxygen anion (O − )-rich MgO−Ni catalyst based on a combined theoretical and experimental approach, which achieves a bis(hydroxyethyl) terephthalate yield of 93.7 % with no heavy metal residues detected. DFT calculations and electron paramagnetic resonance characterization indicate that Ni 2+ doping not only reduces the formation energy of oxygen vacancies, but also enhances local electron density to facilitate the conversion of adsorbed oxygen into O − . O − plays a crucial role in the deprotonation of ethylene glycol (EG) to EG − (exothermic by −0.6 eV with an activation barrier of 0.4 eV), which is proved effective to break the PET chain via nucleophilic attack on carbonyl carbon. This work reveals the potential of alkaline earth metal-based catalysts in efficient PET glycolysis.
研究领域:
材料科学
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催化
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环境科学
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化学工程
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高影响因子
POLYMER DEGRADATION AND STABILITY
·
2021
·
IF 5.03
Tianlin Wang,Xu Gong,Chuanchao Shen,Guangren Yu,Xiaochun Chen
The accumulation of waste PET leads to serious environmental problem. PET degradation has been hot topic and is studied by lots of researchers. At present, numerous catalysts have been developed, among which ionic liquid catalyst is attractive due to its excellent advantages like convenient recycling and highly catalytic effect. In this work, a series of ionic liquids based on 1,1,3,3-tetramethylguanidine (TMG) were synthesized and used as catalyst of PET degradation. The influence of different structure of cation and different metal salt on PET degradation were studied. DFT calculation showed that the interaction between the ionic liquid and ethylene glycol can be changed by adjustment of the structure of the cation. At optimal condition, using [C 6 TMG]Cl/2ZnCl 2 as catalyst, PET conversion was 100% and BHET yield was 92.7%. To our best knowledge, this is first report about ionic liquid catalyst of PET degradation with superior BHET yield. Catalytic effect of [C 6 TMG]Cl/2ZnCl 2 did not obviously decrease after it was reused for six times. Moreover, the degradation of commercial beverage bottles was investigated using [C 6 TMG]Cl/2ZnCl 2 as the catalyst, the BHET yield of 84% was obtained, and the quality purity of the product was 90%. In addition, possible mechanism was explored.
研究领域:
环境科学
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材料科学
·
化学工程
·
催化
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DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2023
·
IF 13.6
Xuejing Xiao,Ruixue Guo,Yumeng Qi,Junyan Wei,Nannan Wu,Shengnan Zhang,Ruijuan Qu
In this study, TiO 2 nanospheres prepared by the sol-gel method were found to efficiently catalyze the photodegradation of 1-butyl-2,3-dimethylimidazolium bromide salt ([BMMIm]Br) under simulated solar irradiation through the main attack of hydroxyl radicals (•OH). The promoting effect of alkali metal (Li + →Cs + ) and alkaline earth metal ions (Mg 2+ →Ba 2+ ) was particularly emphasized. In-situ EPR tests showed that the introduction of alkali and alkaline earth metal ions could enhance the formation of •OH thus leading to a 7%−30.3% increase in the degradation efficiency of. [BMMIm] + . Moreover, the removal efficiency of [BMMIm] + still reached > 96.19% in four real waters. A total of 23 products of [BMMIm]Br were detected, and hydroxyl substitution, bond breaking, direct oxidation and ring opening were considered as the main reactions during the photocatalytic degradation process. The results of toxicity evaluation showed that hydroxylation was a reaction process of increasing toxicity, while the bond breaking reaction had great detoxification capacity for [BMMIm] + . These findings may enhance our understanding on the effects of alkali or alkaline earth metal ions on the photocatalytic activity of TiO 2 , which could also provide reference for the efficient and green removal of alkylimidazolium ionic liquids in waters.
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高影响因子
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