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Catalysis Science & Technology · 2022 ·Vol. 13 ·期 3 ·705-713 · IF 6.177

Ag nanoparticles in the cages of MIL-101(Cr) as an efficient and stable photocatalyst for nitrogen reduction reaction

Xu Zhang,Xiaoman Li,Senda Su,Mengyao Tan,Guodong Liu,Yingying Wang,Min Luo

The active sites of the catalyst and the charge transfer during the reaction are crucial for the photocatalytic nitrogen reduction reaction (PNRR). Here, ultrafine Ag Nanoparticles (Ag NPs) as the active sites and the electron transporters are successfully fixed in the cavities of the metal–organic frame MIL-101(Cr) by the “double solvent-photoreduction” method. The hydrophilic cages of MIL-101(Cr) could restrict and disperse the growth of Ag NPs, and the windows of the cages prevent them from being detached from the MOF carriers. The Schottky junction between Ag NPs and the MIL-101(Cr) leads to ligand–metal charge transfer (LMCT), while the localized surface plasmon resonance effect (LSPR) possessed by Ag NPs themselves generates hot electrons. Thus, N2 was converted to NH3 by the synergistic effect of the two mechanisms, which was 12 times higher than that of pure MIL-101(Cr) and reached 138.81 μmol g−1 h−1. Furthermore, the mechanism of nitrogen fixation and the reason for the stabilization of this catalyst were investigated, and the results were verified by density functional theory calculations.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Imidazolium functionalized polysulfone/DTPA-chitosan composite beads for simultaneous removal of Cr(VI) and Cu(II) from aqueous solutions

Xiaojie Zhang,Kangrui Ma,Hong Peng,Yuefa Gong,Yanjun Huang

Simultaneous removal of chromium(VI) oxyanions and heavy metal cations from contaminated water body is of great significance. In this work, a novel and bifunctional sorbent, imidazolium functionalized polysulfone/DTPA-chitosan composite bead (IMPSF/DACS) was successfully constructed by phase inversion method and applied for co-removal of Cr(VI) and Cu(II) from aqueous solutions. The maximum adsorption capacities for Cr(VI) and Cu(II) on IMPSF/DACS in single system at pH 5 were 56.72 and 43.05 mg g −1 , respectively. In binary system, the removal of Cr(VI) could be further enhanced by the presence of Cu(II) due to the electrostatic shielding effect, while Cu(II) sorption was not significantly affected by the coexistence of Cr(VI). Moreover, IMPSF/DACS could simultaneously reduce low concentrations of Cu(II) and Cr(VI) in simulated contaminated lake water below the limit, while also showing good reusability in co-removal of Cr(VI) and Cu(II). The order of inhibitory effect of competing anions on Cr(VI) removal was as follows: H 2 PO 4 − < Cl − < NO 3 − < SO 4 2− , while the competing hardness cations had a little effects on the adsorption of Cu(II), implying that the Cr(VI) removal was mainly depended on the electrostatic attraction between Cr(VI) and imidazolium ions modified on IMPSF/DACS, and Cu(II) uptake was associated with chelation of DACS encapsulated in IMPSF/DACS beads. These assumptions were confirmed by XPS, FTIR and EDS-mapping techniques.

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MICROPOROUS AND MESOPOROUS MATERIALS · 2023 · IF 5.2

Al and Cr ions co-doped spinel manganese lithium ion-sieve with enhanced Li+ adsorption performance and structural stability

Yuwen Gao,Shougui Wang,Fei Gao,Changqing Guo,Jipeng Dong,Guanghui Chen

The Li 1.6 Mn 1.6 O 4 driven lithium ion-sieve (LIS) is considered as a potential adsorbents for recovering Li + ions from brines owing to their good theoretical adsorption performance and excellent adsorption selectivity. However, the poor cycle stability and the decrease of adsorption capacity resulting from the manganese dissolution loss limit its practical applications. In this work, to mitigate this issue, several novel Al and Cr co-doped manganese LISs were prepared by a facile hydrothermal synthesis method, followed by the acid treatment. The characterization results show that Al and Cr ions are uniformly doped into the spinel crystal structure of LIS, and the introduction of Al and Cr ions can cause the crystal shrinkage, decrease the Mn 3+ content, and raise the mean valence of manganese in the co-doped samples, effectively improving their structural stability. Compared with un-doped ion-sieve H 1.6 Mn 1.6 O 4 , the optimal co-doped ion-sieve H 1.6 Mn 1.54 Al 0.02 Cr 0.04 O 4 with 2% Al doping and 4% Cr doping possesses a higher lithium adsorption capacity, lower manganese dissolution loss, and stronger cyclic stability. Additionally, the H 1.6 Mn 1.54 Al 0.02 Cr 0.04 O 4 possesses a high adsorption selectivity of Li  +  over Mg 2+ , Ca 2+ , K + and Na + . Furthermore, the lithium adsorption is determined to be a chemical and monolayer adsorption process on the prepared LIS. The good lithium adsorption capacity and adsorption selectivity as well as the good recyclability make the prepared Al and Cr co-doped LIS a promising adsorbent for the efficient lithium recovery form brines.

CAS / MDL: 1310-66-3 7447-41-8
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2022 · IF 8.025

A magnetic MIL-125-NH2@chitosan composite as a separable adsorbent for the removal of Cr(VI) from wastewater

Shichen Wang,Yixuan Liu,Yue Hu,Weibo Shen

Metal-organic frameworks (MOFs) are gradually used since of their huge specific surface area and superior pore structure. However, there are problems such as easy aggregation and difficult separation in water treatment. In this study, we prepared composite microspheres (FMCS-1) by modifying MIL-125-NH 2 with Fe 3 O 4 and chitosan. The structural characterization and performance analysis of the materials showed that the introduction of chitosan effectively prevents the stacking of MOFs. The magnetic test manifested that Fe 3 O 4 solved the problem of the difficult separation of MOFs from water. The removal potential of toxic Cr(VI) was tested by adsorption experiments. The isotherm model indicated that FMCS-1 is a single molecular layer adsorbent with a maximum adsorption capacity of 109.46 mg/g at pH = 2. The adsorption kinetics showed that the adsorption of Cr(VI) by FMCS-1 was chemical adsorption. The acid resistance test demonstrated that FMCS-1 can exist stably in acid solutions. The recycling experiments proved that the adsorbent can be reused and the removal percentage still reaches 50 % after 5 cycles. This work expands the application of MOFs in water treatment and also provides an effective adsorbent for Cr(VI) removal.

CAS / MDL: 9012-76-4
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APPLIED SURFACE SCIENCE · 2023 · IF 6.7

Incorporation of Zr-based metal-organic polyhedron into the PDA/PVDF adsorptive membrane for rapid removal of Cr(VI)

Juan Zhu,Shuang-Bao Li,Bao-Xu Jiang,Yu-Teng Zhang

Zirconium-based metal-organic polyhedra (ZrMOPs) have gained significant attention owing to their well-defined cavities, stability and potential applications. Herein, a novel composite membrane (PDA/ZrT-1-NH 2 /PVDF) was developed by incorporating amino-functionalized ZrMOP (ZrT-1-NH 2 ) into polydopamine (PDA) and trimesoyl chloride (TMC) cross-linking system. Notably, the cationic ZrT-1-NH 2 cages were immobilized onto the membrane surface by a simple vacuum filtration method, which thus endowed the surface positive charge for the membrane. A pre-prepared composite membrane was used to remove Cr(VI) from the wastewater. The effects of pH, contact time, initial Cr(VI) concentration, temperature, coexisting ions competition and reusability were investigated in batch experiments. The results revealed the as-prepared composite membrane exhibited high removal efficiency of 96.6 % for Cr(VI) ions within 5 min. In addition, the adsorption rate was very fast, reaching adsorption equilibrium in less than 30 min. Finally, a possible adsorption mechanism was proposed. The adsorption process was dominated by physical adsorption accompanied by a partial reduction of Cr(VI) to Cr(III).

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Journal of Materials Research and Technology-JMR&T · 2023 · IF 6.4

Research of TE behaviour and compression property of porous Ni–Al–Cr intermetallic compounds in the β phase region

Yang Yu,Baojing Zhang,Xiaoping Cai,Zhejian Cao,Farid Akhtar,Xinyang Jiao,Xueding Chai,Peizhong Feng

Ni–Al–Cr alloys in the β phase (B2–NiAl) region exhibit remarkable stability and mechanical property. Through thermal explosion (TE) reaction, Ni–Al–Cr intermetallic compounds with high porosity can be obtained. In this study, the focus lies on analyzing the macroscopic morphology, microstructure, phase distribution, TE behaviour, and the mechanical property of porous Ni–Al–Cr in the β phase region. Following the TE reaction, the Al-rich sintered product demonstrates a uniform phase composition and high porosity, reaching 44.39%. The vigorous TE reaction promotes the formation of interconnected pores, while the high porosity structure compromises the mechanical properties of the sample. Conversely, the Al-poor sintered product, due to a moderate TE reaction and low porosity structure, maintains its complete morphology and exhibits excellent compression resistance (yield stress reaching 538 MPa). This study offers valuable insights for the fabrication of porous Ni–Al–Cr materials with exceptional structure and performance.

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LANGMUIR · 2023 · IF 3.9

Physicochemical Effects of Sulfur Precursors on Sulfidated Amorphous Zero-Valent Iron and Its Enhanced Mechanisms for Cr(VI) Removal

Zishen Lin,Jiang Xu,Aibin Zhu,Chi He,Changzhao Wang,Chunli Zheng

Amorphous zerovalent iron (AZVI) has gained considerable attention due to its remarkable reactivity, but there is limited research on sulfidated amorphous zerovalent iron (SAZVI) and the influence of different sulfur precursors on its reactivity remains unclear. In this study, SAZVI materials with an amorphous structure were synthesized using various sulfur precursors, resulting in significantly increased specific surface area and hydrophobicity compared to AZVI. The Cr(VI) removal efficiency of SAZVI-Na2S, which exhibited the most negative free corrosion potential (−0.82 V) and strongest electron transfer ability, was up to 8.5 times higher than that of AZVI. Correlation analysis revealed that the water contact angle (r = 0.87), free corrosion potential (r = −0.92), and surface Fe(II) proportion (r = 0.98) of the SAZVI samples played crucial roles in Cr(VI) removal. Furthermore, the enhanced elimination ability of SAZVI-Na2S was analyzed, primarily attributed to the adsorption of Cr(VI) by the FeSx shell, followed by the rapid release of internal electrons to reduce Cr(VI) to Cr(III). This process ultimately led to the precipitation of FeCr2O4 and Cr2S3 on the surface of SAZVI-Na2S, resulting in their removal from the water. This study provides insights into the influence of sulfur precursors on the reactivity of SAZVI and offers a new strategy for designing highly active AZVI for efficient Cr(VI) removal.

CAS / MDL: 1317-37-9
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JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

In-situ synthesis of direct Z-scheme 2D/2D ZnIn2S4@CeO2 heterostructure toward enhanced photodegradation and Cr(VI) reduction

Qiang Gao,Junxi Li,Bin Liu,Chenguang Liu

The rationally designed semiconductor photocatalytic materials have attracted significant attention because of their huge advantages in the use of solar light. Herein, a series of direct Z-scheme heterojunction nanocomposites were synthesized via in situ growth of zinc indium sulfide nanosheets on ceria nanosheets (ZnIn 2 S 4 @CeO 2 ) and employed for effective photodegradation and Cr(VI) reduction. Advanced characterizations such as XPS , EPR spectra, and DFT calculations verified that the formation of direct Z-scheme charges transfer mechanism promoted rapid charge separation and retained strong redox capacity. As a result, the optimized ZnIn 2 S 4 @CeO 2 sample showed significantly promoted photocatalytic removal rates for tetracycline (TC) and Cr(VI) at a 3.7 and 4.5 times enhancement by comparison with the pristine ZnIn 2 S 4 , respectively. Additionally, after four consecutive cyclic tests, the as-synthesized nanocomposite exhibited remarkable photocatalytic activity and stability. The present work provides an integrated engineering strategy for Z-scheme photocatalyst systems with high photocatalytic efficiency and extensive applications.

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Frontiers in Energy Research · 2022 · IF 3.858

Biochar-embedding iron-alginate microspheres derived from bagasse by one-step microwave pyrolysis/activation for enhanced Cr(VI) removal

Wang Hongfei,Zhao Xiqiang,Yang Xinfei,Sun Shuang,Wang Wenlong,Mao Yanpeng,Song Zhanlong

In this paper, two types of adsorption materials SA-C-Fe and SA-C-Fe(C) were prepared using bagasse biochar produced by one-step microwave pyrolysis and activation for Cr(VI) removal of wastewater. The adsorption materials were characterized, and Cr(VI) adsorption performance, kinetics and thermodynamics on adsorption materials were studied. Results show that microwave pyrolysis/activation contributes to developed pore structure and abundant active functional groups, resulting in high Cr(VI) adsorption capacities. The optimal preparation conditions for biochar is: microwave power 500 W, ZnCl2/bagasse ratio 2.5:1 and pyrolysis/activation time 15 min, and the specific surface area of biochar is 1,787.64 m2/g. The Cr(VI) adsorption of the two materials is more in line with the pseudo-second-order kinetic model, and the adsorption process is dominated by chemical adsorption. The static removal experiment of Cr(VI) using SA-C-Fe and SA-C-Fe(C) has the best removal effect at pH = 2, and the whole adsorption process is more in line with the Langmuir-Freundlich isotherm model. Calculated by the pseudo-two-order kinetic model and the Langmuir-Freundlich isothermal model, the maximum adsorption rate for Cr(VI) of SA-C-Fe and SA-C-Fe(C) are 211.87 mg/g and 388.92 mg/g, respectively. The removal process is mainly dominated by three mechanisms: electrostatic adsorption, ion exchange and redox reactions. The improvement of Cr(VI) adsorption capacity is attributed to more developed pore structure. The results offer beneficial reference for the application of low-cost carbon-based adsorption materials for pollutants separation, and effectively realize the utilization of bagasse pyrolysis by-products.

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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2022 ·Vol. 30 ·期 10 ·26889-26900 · IF 5.19

Properties and mechanism of Cr(VI) removal by a ZnCl2-modified sugarcane bagasse biochar–supported nanoscale iron sulfide composite

Jiang Chunlu,Zhou Shijia,Li Chang,Yue Fengdie,Zheng Liugen

A ZnCl 2 -modified biochar-supported nanoscale iron sulfide composite (FeS-ZnBC) was successfully prepared to address the easy oxidization of FeS and enhance Cr(VI) removal from water. The material was characterized by SEM, XRD, FTIR, and XPS. The effects of FeS:ZnBC mass ratio, FeS-ZnBC dosage, solution pH, initial Cr(VI) concentration, and reaction time on the adsorption performance were investigated. The results revealed that the optimum adsorption capacity of FeS-ZnBC (FeS:ZnBC = 1:2) for Cr(VI) was 264.03 mg/g at 298 K (pH = 2). A Box-Behnken design (BBD) was applied to optimize the input variables that affected the adsorption of Cr(VI) solution. The results revealed that the highest removal (99.52%) of Cr(VI) solution was achieved with a Cr(VI) initial concentration of 150.59 mg/L, FeS-ZnBC adsorbent dosage of 2 g/L, and solution pH of 2. The sorption kinetics could be interpreted using a pseudo-second-order kinetic model. The isotherms were simulated using the Redlich-Peterson isotherm model, indicating that Cr(VI) removal by the FeS-ZnBC composites was a hybrid chemical reaction-sorption process. The main mechanisms of Cr(VI) removal by FeS-ZnBC were adsorption, chemical reduction, and complexation. This study demonstrated that FeS-ZnBC has potential application prospects in Cr(VI) removal.

CAS / MDL: 7646-85-7
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Construction of microspherical flower-like Zn3In2S6-BGQDs/AgBr S-scheme heterojunction for photocatalytic elimination of nitrofurazone and Cr (VI)

Jiangli Sun,Jinhang Yang,Jiaxiang Liang,Lingli Tu,Yuejing Bin,Yanping Hou

It is crucial to design efficient photocatalysts for elimination of combined pollutants in wastewater. Herein, the S-scheme Zn 3 In 2 S 6 -BGQDs/AgBr (ZBA) heterojunction was synthesized through co-modification of Zn 3 In 2 S 6 with B-doped graphene quantum dots (BGQDs) and AgBr nanoparticles using solvothermal method for synchronous removals of nitrofurazone (NFZ) and Cr (VI). Characterization results revealed that ZBA showed superior photocatalytic activity than the counterparts. In NFZ-Cr (VI) coexistence environment, removal efficiencies towards NFZ and Cr (VI) were 95.23% and 99.39% using the ZBA photocatalyst within 2 h of visible light irradiation. Results demonstrated that ∙OH, h + and ∙O 2 − played major role for NFZ removal, while mainly e - and ∙O 2 − contributed to Cr (VI) reduction. The S-scheme heterojunction mechanism of ZBA was confirmed by energy band structure analysis, ESR and calculated work function.   Possible pathways and mechanisms of NFZ degradation were proposed according the identified intermediates. Besides, the ecotoxicity of intermediates was analyzed. This study advances the development of photocatalytic treatment of combined-polluted wastewater.

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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

New method for efficient removal of Cr(VI) by recoverable magnetic nitrogen-doped carbon aerogel microspheres: Kinetics and mechanism

Shiyao Li,Rong Cheng,Jiahao Li,Haobo Hou,Yi Wang,Jiaao Chen,Yuwei Xiang,Min Zhou

The efficient removal of hexavalent chromium from solution is a challenging task, in this paper, the nZVI and nitrogen co-doped magnetic carbon aerogel microsphere composites (nZVI@NCAs) were prepared via the microemulsion polymerization and subsequent carbonization process, and were expected to satisfactory performance in the removal of Cr(VI). From batch experiments, the Cr(VI) removal process by nZVI@NCA900 fitted better with the pseudo-second-order model. The optimal nZVI@NCA900 was superior to that of most magnetic carbon-substrate composites, displaying high Cr(VI) adsorption capacity of 266.79 mg·g −1 at 318 K. Additionally, it was found that Cr(VI) was reduced to the low-toxicity Cr(III) from the results analyzed by XPS, and nZVI@NCA900 exhibited Cr(VI) reduction performance of 33.92% Cr(VI) reduced to Cr(III). The reaction between the nZVI@NCAs and Cr(VI) was pH-dependence, endothermic and spontaneous. Removal mechanisms might involve multiple processes. The nZVI particles on the surface acted as reductants to reduce Cr(VI) to Cr(III) and form Cr(III)/Fe(III) hydroxides to precipitate on nZVI@NCAs. Simulation results by DFT prove that N is an active site and show positive effect in the adsorption system. N atoms were used as active sites to stabilize the interaction with Cr(VI) via adsorption attributed to electrostatic and act as electron donors for reduction of Cr(VI). The nZVI particles encapsulated by carbon aerogels could provide magnetic stability after acid reaction, which was beneficial to the separation of adsorbents after reaction and reuse for many cycles. These results provide a new view for developing magnetic carbon materials to remove Cr(VI) from contaminated water.

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