ANALYTICAL CHEMISTRY
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2015
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IF 5.636
Juan Wei,Zheng Guo,Xing Chen,Dong-Dong Han,Xiang-Ke Wang,Xing-Jiu Huang
Detection of Cr(VI) by electrochemical methods generally focuses on noble-metal-modified electrodes in strong acid solution using voltammetric techniques. In this work, we report a new strategy to detect Cr(VI) as HCrO4– at pH 5.0 in drinking water using electrochemical impedance spectroscopy. The strategy is based on the high-affinity and specific binding of crown ethers (i.e., azacrown) to HCrO4–, which forms sandwich complexes between them via hydrogen bonds and moiety interactions with K+ captured by azacrown on its self-assembled Au electrode surface. This then blocks the access of redox probes (Fe(CN)63–/4–) to the self-assembled Au electrode, further resulting in an increase in the electron transfer resistance. This method offers a detection limit of 0.0014 ppb Cr(VI) with a sensitivity of 4575.28 kΩ [log c (ppb)]−1 over the linear range of 1–100 ppb (R2 = 0.994) at pH 5.0. In addition, the azacrown self-assembled Au electrode has good selectivity for Cr(VI) with good stability and low interferences. This approach can be performed on spiked Cr(VI) as well as real samples. To the best of our knowledge, this is the first example of electrochemical impedimetric sensing that allows ultrasensitive and ultraselective detection of Cr(VI).
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2022
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IF 9.965
Senda Su,Xiaoman Li,Xu Zhang,Jingting Zhu,Guodong Liu,Mengyao Tan,Yingying Wang,Min Luo
The incorporation of polyoxometalates (POMs) in metal-organic frameworks (MOFs) with host-guest structure have proven to be effective strategy to rational design of heterogeneous catalysis. In this study, the Keggin-type POM@MIL-101(Cr) composite catalysts (PMo 12 , PW 12 and SiW 12 ) are synthesized for nitrogen fixation reaction without sacrificial agents at room temperature in the first time. The SiW 12 molecules are encapsulated in smaller cavities of MIL-101(Cr) by solvothermal method and in larger cavities by impregnation method, respectively. Solvothermal synthesized catalyst has a performance of 75.56 μmol·h −1 ·g -1 cat and TOF value of 1.95 h −1 , which are about 10 and 88 times than that of Na 4 SiW 12 O 40 . The excellent performance is ascribed to the synergistic effect of SiW 12 and MIL-101(Cr). The MIL-101(Cr) adsorbs a large amount of N 2 and generates sufficiently photogenerated electrons under sunlight irradiation, and electrons quickly transfer to the SiW 12 through hydrogen bonds. Moreover, the agglomeration effect of the homogeneous catalyst SiW 12 is weakened due to encapsulation with more exposed active sites. This work provides a feasible route to design and synthesize nanocomposite materials with exceptional performance for photocatalytic nitrogen fixation.
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RSC Advances
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2024
·Vol. 14
·期 8
·5142-5148
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IF 3.9
Chunhong Jin,Jingchao Liu,Yilin Yin,Zenghe Li
In wastewater containing heavy metals, Cr(VI) is a potentially toxic metal, mainly derived from production and processing processes such as textile printing, dyeing, ore mining, battery applications, metal cleaning and electroplating. WO3 is widely used in photocatalytic degradation and reduction, and its utilization rate of visible light is high. However, the rapid recombination of photogenerated electron–hole pairs of WO3 limits its use. In this work, the composite material (WxMy) of WO3 and MIL-125 (Ti) was prepared by the ball milling method, and the catalyst was used to photocatalytically reduce Cr(VI). After using W90M10 as a photocatalyst for 50 min, the reduction rate of Cr(VI) can reach 99.2%, and the reduction rate is 2.3 times that of WO3. After 5 cycles of use, the reduction rate can still reach 91.3%. It is mainly due to the formation of a II-type heterojunction between WO3 and MIL-125 (Ti), which promotes the separation of photogenerated electron–hole pairs, thus improving the efficiency of photocatalytic reduction of Cr(VI).
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ELECTROCHIMICA ACTA
·
2025
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IF 5.6
Lei Zhou,Xiayuan Yang,Xin Zhang,Mingzhe Li,Kepi Chen,Yuzhen Lv,Jin Zhang,Wei Zhou
It is of great significance to develop energy-saving and scalable synthetic methods for high-performance electrodes in green hydrogen production. Here we report a green room-temperature synthesis to produce integrated electrode with Cr-doped NiFe LDH/FeOOH nanosheets grown on iron foam. This simple one-step corrosion strategy can fabricate the electrode with an area up to 600 cm 2 . Through in situ self-activation process, the obtained Cr v -NiFeOOH/FeOOH@IF electrode exhibits excellent OER activity and durability, offering ultralow overpotentials of 279.3 and 308.4 mV to drive high current densities of 500 and 1000 mA cm −2 and operating steadily at industrial-level current density of 1000 mA cm −2 over 200 hrs with a high potential retention of 98.2 %. In situ electrochemical tests and theoretical calculations reveal the synergistic kinetics modulation. Both Cr vacancies and NiFeOOH/FeOOH heterostructure can accelerate water oxidation process by optimizing the adsorption energy of the intermediates. DFT calculations confirm Cr vacancies can further reduce the rate-determining step (RDS) energy barrier of the heterostructure. This work offers an economical and scalable corrosion strategy to produce high-efficient OER electrocatalysts toward industrial water splitting.
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CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Shu Chen,Linping Chen,Xiaoqian He,Ruoxi Wu,Chang Peng
Smart adsorbents with responsive self-healing ability will be promising, as they can meet the desirable requirements of sustainable and efficient usage in water treatment. Herein, a photo-induced self-healing gel adsorbent is fabricated by the combination of transition metal carbides Ti 3 C 2 T x (MXene), polyethyleneimine (PEI), and poly(N,N-dimethylacrylamide) (PDMAA) for sustainable and efficient removal of specific target Cr(VI) from water. PEI, as a potent adsorptive motif, endows the gel with high maximum adsorption capacity ( q m ) (i.e., ∼300 mg g −1 for Cr(VI)). Crucially, leveraging the photothermal conversion of Ti 3 C 2 T x and the self-healing repair of PDMAA, the gel is imbued with rapid photo-induced self-healing ability, which facilitates its sustainability in adsorption application. The photoinduction applied to the damaged gel adsorbent enables its rapid self-healing repair, as well as maintains its efficient removal efficiency for reapplication, which makes it more suitable for long-time usage in environments. This work provides a new insight into the application of smart adsorbents for sustainable and efficient adsorption in the field of wastewater treatment.
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CHEMOSPHERE
·
2018
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IF 4.427
Wei Fang,Xianying Jiang,Hanjin Luo,Junjie Geng
A novel hybrid nanocomposite, polypyrrole nanoparticles (PPy) anchored on the graphene/silica nanosheets with the high specific surface area (polypyrrole-graphene/silica, GS-PPy), was synthesized by a facile in situ polymerization and shows great potential to remove hexavalent chromium [Cr(VI)] in aqueous solutions. Characterizations by XRD , TEM, SEM, BET, FT-IR and XPS, have confirmed that the PPy nanoparticles were well-distributed on the surface of GS nanosheets . The effects of pH, contact time, the concentration of Cr(VI), temperature, coexisting ions and the number of adsorption-desorption cycles were studied. The maximum adsorption capacity of the GS-PPy for Cr(VI) was 429.2 mg g −1 at 298 K at pH 2, which was much higher than PPy nanoparticles and other related materials. The adsorption data fitted to the pseudo-second-order model and Langmuir isotherm model. The removal mechanism involved in electrostatic attraction, ion exchange and reduction process that partial adsorbed Cr(VI) was reduced to Cr(III). And Cr(III) was still retained on the surface of GS-PPy. The GS-PPy nanocomposite will be a potential candidate for the removal of Cr(VI) from the industrial waste water.
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ENVIRONMENTAL TECHNOLOGY
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2020
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IF 2.213
Liang Xu,Fenglian Fu,Peijing Yu,Guangzhao Sun
To efficiently treat hexavalent chromium (Cr(VI)) wastewater, K2FeO4 was used to remove and reduce Cr(VI) in presence of Mn(II) in this paper. Batch removal experiments were carried out to study the effect of Fe/Mn molar ratios, initial pH, in-situ and ex-situ and co-existing ions on Cr(VI) removal. The results showed the removal efficiency of Cr(VI) was 97.7% for the initial Cr(VI) concentration of 10.0 mg/L at Fe/Mn molar ratio of 2:3 and initial pH 8.0. Meanwhile, the high removal efficiency of Cr(VI) had been maintained throughout the pH range of 3.0–8.0 in the experimental study. Moreover, the removal process was relatively stable regardless of in-situ and ex-situ, and co-existing ions such as Ca2+ and low concentration of HCO3− had no intense effect on Cr(VI) removal, while SO42− inhibited Cr(VI) removal in the reaction system. To investigate the removal mechanism of Cr(VI) by K2FeO4 in presence of Mn(II), the reaction products were characterized by the Fourier transformed infrared spectrometer, X-ray powder diffraction, Transmission electron microscopy and the high-resolution X-ray photoelectron spectroscopy. The results indicated the ferrate decomposition products of γ-FeOOH/γ-Fe2O3 had the ability to adsorb Cr(VI) and react with Mn(II) to form γ-Fe2O3-Mn(II) complex to adsorb and reduce Cr(VI).
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Nano Energy
·
2026
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IF 16.7
Yan Zheng,Linjing Qiao,Zhongyang Wang,Hao Gong,Boyu Liu,Jiajun Wang,Liping Tong,Zhiyuan Zhao,Xiao Zhou,Tongxiang Fan
Chemical pressure engineering of Jahn-Teller distortion enables broadband high emissivity. • A quantitative Jahn-Teller distortion index ( Q OJT ) is established to correlate structure with emissivity. • Ca 2+ doping (Cu, Cr, Mn) 3 O 4 spinel achieves an emissivity of 0.947 across the 0.4–25 μm range. • Exceptional thermal stability is demonstrated with less than 1.4% degradation at 1673 K. • An 11% enhancement in heating rate is achieved in practical radiative heating tests. Infrared radiation materials with broadband emissivity and high thermal stability are highly desirable for energy saving and thermal management applications. However, achieving high emissivity across the visible to mid-infrared range (0.4–25.0 μm) remains challenging due to the discontinuous absorption mechanisms in ceramics. Herein, a strategy based on promoting Jahn-Teller (JT) distortion is proposed to enhance the broadband emissivity of (Cu, Cr, Mn) 3 O 4 spinel. Substituting Cu 2+ with alkaline-earth ions (Mg 2+ , Ca 2+ , Sr 2+ ) introduces tunable chemical pressure, which modifies the local electric field and valence state distribution, thereby regulating the JT structural evolution. An octahedral JT structural descriptor ( Q OJT ) is developed to quantitatively compare JT structural evolution among different compositions. The Q OJT values show a positive correlation with broadband emissivity. The optimized JT structural evolution simultaneously enhances electronic transition, carrier and lattice vibration absorption, enabling synergistic regulation of broadband emissivity across the entire 0.4–25.0 μm spectral range. Among the investigated compositions, Ca 2+ -doped (Cu, Cr, Mn) 3 O 4 exhibits a broadband emissivity of 0.947 and maintains excellent stability under a simulated hypersonic environment at 1673 K. In radiative heating test, it achieves a heating rate approximately 11% higher than that of Al 2 O 3 . These findings demonstrate that chemical pressure provides an effective strategy for regulating JT structural evolution and designing broadband thermal radiation ceramics for high temperature applications. Download: Download high-res image (225KB) Download: Download full-size image Chemical-pressure-tuned Jahn-Teller distortion in (Cu, Cr, Mn) 3 O 4 spinel enables broadband high emissivity (0.947, 0.4–25.0 μm) and exceptional thermal stability up to 1673 K. A quantitative octahedral Jahn-Teller distortion index ( Q OJT ) correlates directly with emissivity performance. The optimized material achieves a 11% acceleration in heating rate, demonstrating its potential for high-temperature radiative transfer and thermal management applications.
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ChemPlusChem
·
2026
·Vol. 91
·期 8
·e70223
·
IF 3.1
Huan V Doan,Huong T T Tran,Duyen T Le,Xuan N Pham
In this study, a novel Ni–MoO 3 @MIL‐101(Cr) composite catalyst was synthesized via a one‐step hydrothermal method for the oxidative desulfurization (ODS) of dibenzothiophene (DBT). The catalyst combines the high specific surface area of MIL‐101(Cr) with the redox properties of Ni–MoO 3 , providing an effective synergy between adsorption and catalytic oxidation. The incorporation of Ni as a promoter significantly enhances catalytic activity, enabling complete sulfur removal (∼100%) under mild conditions (50 °C) within 60 min. Structural characterizations (scanning electron microscopy, X‐ray diffraction, and SAED) reveal that the catalyst retains its nanosheet–nanorod morphology and crystalline MoO 3 phase after repeated use, with only a slight decrease in the crystallinity of the MIL‐101(Cr) framework. Mechanistic analyses using X‐ray photoelectron spectroscopy, Raman, and temperature‐programmed reduction demonstrate that surface oxygen vacancies and Lewis acid sites promote ODS activity, while highly dispersed Ni–MoO 3 species facilitate H 2 O 2 activation and Mo 6+ /Mo 5+ redox cycling, leading to efficient generation of reactive oxygen species. The catalyst also exhibits excellent stability, maintaining 98.7% DBT conversion after five cycles. These results demonstrate that the strong Ni–Mo synergistic effect and efficient oxygen activation make Ni–MoO 3 @MIL‐101(Cr) a robust and highly efficient catalyst for deep fuel desulfurization. This study presents a significant advancement in the field of oxidative desulfurization by developing a synergistic Ni–MoO 3 redox catalytic system confined within the porous MIL‐101(Cr) framework. Unlike conventional catalysts, the designed material effectively enhances H 2 O 2 activation through cooperative interactions between Ni and Mo species, enabling rapid and ultra‐deep removal of refractory sulfur compounds under mild conditions. The integration of redox‐active sites with a high‐surface‐area MOF support not only improves catalytic efficiency but also ensures excellent stability and recyclability. This work provides new insights into the rational design of bimetallic catalysts for green fuel purification and offers a promising strategy for achieving sustainable and energy‐efficient desulfurization processes.
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MICROPOROUS AND MESOPOROUS MATERIALS
·
2026
·
IF 4.5
Yan Jin,Hui Zhang,Tengfei Li,Shaojie Lei,Meier Jiaerheng,Dezhang Ren,Zhibao Huo
Biodiesel has emerged as a promising alternative to conventional diesel due to its renewability and environmental friendliness. In this study, a MIL-101(Cr) featuring synergistic acid sites was developed through a combined defect engineering and post-sulfonation strategy, enabling efficient esterification of oleic acid under mild conditions. Defects were introduced in the MIL-101(Cr) through a mixed-ligand approach. The existence of abundant oxygen vacancies in the defect-engineered MIL-101(Cr) was confirmed by electron paramagnetic resonance (EPR), which could provide adequate grafting sites for the subsequent sulfonation. The sulfonic acid-functionalized MIL-101(Cr) catalyst (MRBSX) was then synthesized by post-sulfonation with chlorosulfonic acid as the sulfonation agent. The chemical structure and sulfonic acid density of MRBSX were systematically investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), brunauer-emmett-teller (BET), and Fourier-transform infrared spectra (FT-IR), and other characterization techniques. Acid-base titration combined with elemental analysis (EA) demonstrated the successful loading of sulfonic acid groups in MRBSX, highlighting the promotional role of oxygen vacancies in enhancing acid site density and catalytic efficiency. Under optimized reaction conditions (100 °C, 6 wt%, 3 h, and M/O = 8:1), the MRBSX with 10 mol% benzoic acid achieved a high oleic acid conversion of 96.7 % and a corresponding biodiesel yield of 91.5 %. Therefore, the proposed synergistic strategy of defect engineering and post-sulfonation is effective in constructing high-performance solid acid catalysts, demonstrating promising potential in green energy conversion applications.
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APPLIED SURFACE SCIENCE
·
2026
·
IF 6.6
Yulong Xiang,Xinbin Ji,Xiaoli Dong,Yu Wang,Nan Zheng,Jialin Niu,Pei Yu,Chumin Yan
As Cr(VI) pollution intensifies, the development of efficient, eco-friendly, and sustainable treatment technologies has become a vital focus in environmental science. Photocatalytic reduction is often seen as a promising approach for removing Cr(VI), thanks to its low energy requirements and minimal environmental impact. However, traditional photocatalytic materials face significant challenges, including narrow photoresponse range and high rate of electron-hole recombination, which impede their practical efficiency. In this study, we successfully synthesized Fe-DUT-67 photocatalysts by incorporating Fe single atoms into the zirconium-based metal–organic framework (DUT-67) through post-synthetic modification. A significant enhancement in both the visible-light absorption capacity and carrier separation efficiency of the as-prepared Fe-DUT-67 has been observed, attributed to the formation of Fe-O coordination bonds between the Fe atoms and Zr-O clusters. Fe-DUT-67-2 exhibited impressive Cr(VI) reduction activity under full-spectrum illumination, with a remarkable 90% reduction efficiency of Cr(VI) within 18 min. Density functional theory (DFT) calculations shed light on the crucial role of Fe sites in promoting photoelectron transport and facilitating Cr(VI) reduction. This work not only presents an efficient photocatalytic material for alleviating Cr(VI) pollution but also provides a theoretical foundation and design principles for the development of high-performance catalytic systems utilizing single-atom modified metal–organic frameworks.
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RESEARCH ON CHEMICAL INTERMEDIATES
·
2026
·
IF 3.3
Xiang Yulong,Ji Xinbin,Dong Xiaoli,Wang Yu,Zheng Nan,Luo Yang,Zhao Honglin,Yan Chumin
Charge separation, transfer, and recombination are crucial factors that influence the efficiency of photocatalytic Cr(VI) reduction. The construction of Schottky junctions can remarkably facilitate the spatial separation of charge carriers. To address the issue of heavy metal pollution in industrial wastewater, an Ag-DUT-67 Schottky junction photocatalyst was synthesized by depositing silver nanoparticles (Ag NPs) onto the DUT-67 surface through a photoreduction technique. The findings indicate that Ag NPs are evenly distributed and coordinated with the sulfur atoms in the DUT-67 ligands. This modification not only elevates the oxygen vacancy content but also broadens the light response range. A Schottky barrier is established at the Ag-DUT-67 interface, which effectively reduces carrier recombination. Notably, Ag-DUT-67–2 demonstrates a remarkable Cr(VI) reduction efficiency of 98% within 30 min, with a reaction rate that is 3.4 times as much as pristine DUT-67. Additionally, Ag-DUT-67–2 shows excellent stability in high-concentration Cr(VI) solutions and in the presence of interfering ions, coupled with good recyclability. This study offers a novel framework of interface engineering and performance enhancement of MOF-based photocatalysts for heavy metal reduction.
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