CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Weikang Ling,Yushun Han,Huitong Jiang,Huanqiu Wei,Yuchen Ren,Min Hong,Hongdan Zhang,Jiliang Ma,Runcang Sun
Coupling photocatalytic CO 2 reduction with biomass refining offers a sustainable route to produce renewable fuels and value-added chemicals. However, interfacial charge recombination limits its efficiency. Herein, we report a three-dimensional, hierarchical, honeycomb-like carbon nitride framework co-doped with Cu/Co species (Cu x Co y @CN) and enriched with N vacancies, synthesized through a sequential hydrothermal-calcination and in-situ doping strategy. Advanced spectroscopy and in-situ probes reveal the directional electron transfer from Co to Cu sites, creating an electron-rich heterointerface that spatially separates redox centers, namely Cu sites for CO 2 reduction and Co sites for biomass oxidation. The engineered architecture delivers a larger specific surface area (95.40 m 2 g −1 ), extended visible-light absorption (>800 nm), narrowed band gap (to 1.93 eV), and enhanced charge separation (2.27-fold higher photocurrent). The optimized Cu 2 Co 1 @CN catalyst achieves an exceptional CO evolution ratio of 84.8 μmol g −1 h −1 with a xylonic acid yield of 74.0% from xylose, and retains 91.8%/95.2% of its initial CO/xylonic acid activity after eight cycles. Furthermore, the Cu 2 Co 1 @CN catalyst shows broad substrate scope and promising scalability, including sunlight-tracking experiments. This study provides fundamental insights into interfacial charge engineering and presents a viable strategy for synergistically converting solar energy, abundant biomass, and anthropogenic CO 2 into sustainable chemical feedstock.
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CORROSION SCIENCE
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2017
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IF 5.245
Xin Ma,Likun Xu,Wei Wang,Zhifeng Lin,Xiangbo Li
A new type of composite nanoparticles (CNPs) was prepared by loading a typical inhibitor 1-hydroxybenzotriazole (HOBT) for corrosion protection of copper alloy in mesoporous silica nano-containers. The release kinetics of HOBT from CNPs in 3.5% NaCl solution was in conformity with the first order kinetic model. The open circuit potential monitoring, the morphology observation and the scanning Kelvin probe measurement of the Cu-Zn alloy in 3.5% NaCl solution with CNPs proved that a uniformly protective film was formed on the surface. Electrochemical impedance spectroscopy was employed to analyse the corrosion inhibition process of CNPs on the Cu-Zn alloy.
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Journal of Materials Chemistry C
·
2021
·Vol. 10
·期 2
·665-671
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IF 7.393
Dandan Gao,Jiyang Xie,Jian Wang,Wanbiao Hu
It is widely accepted that localized electron hopping induces colossal permittivity in the bulk of transition-metal-based materials. However, the mechanism and the control of the electron hopping process remain to be explored. In this work, the effect of the B-site environment and multiple Cu valence-states on electron hopping were experimentally revealed in the LiCuNb2.95M0.05O9 (M = Mg, Ti) systems. The results demonstrated that Mg/Ti substitution for Nb5+ at the B-site effectively causes multivalent states of A-site Cu cations, i.e. Cu+/Cu2+/Cu3+, and distorted NbO6 octahedra. Upon Mg/Ti substitution, the dielectric permittivity was enhanced by approximately two orders of magnitude (at 1 kHz and 300 K) and an additional dielectric relaxation was induced. More importantly, it was revealed that the B-site substitution effectively adjusted the activation energy and average distances for the electron hopping.
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APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING
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2021
·Vol. 127
·期 10
·1-9
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IF 2.584
Zhang Yu,Cao Ping,Lin Wei,Liu Qiang,Chen Ziyuan,Cao Jun,Yang Guannan,Cui Chengqiang
In this paper, a mixed sintering accelerator of colophony and cetyltrimethyl ammonium bromide (CTAB) was developed to improve the sintering properties of Cu nanoparticles (NPs) paste. With the synergy effect of the mixed sintering accelerator, Cu NPs paste could be well sintered at 260 °C for 30 min under a pressure of 2 MPa, and the shear strength was greatly improved from 15 to 33 MPa. The fracture morphology of the Cu NPs joint transformed from brittle interface failure features to ductile dimple features, and the porosity in the sintered layer was significantly reduced. XRD analysis further confirmed that the synergy of colophony and CTAB could effectively remove the oxides in the Cu NPs paste during sintering, and thereby improve the sintering properties. This work can provide an applicable approach to improve the sintering properties of metal NPs and help to understand the synergy effect of sintering accelerators on the bonding behaviors of metal nanoparticles at low temperatures. Graphic abstract
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SEPARATION AND PURIFICATION TECHNOLOGY
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2022
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IF 9.136
Libing Zheng,Min Tang,Yize Wang,Deyin Hou,Xiaoyu Li,Jun Wang
In this study, a novel Janus membrane was developed by constructing Cu-1,3,5-benzenetricarboxylic acid (Cu-BTC) metal–organic frameworks (MOFs) hydrophilic coating on polyvinylidene fluoride (PVDF) membrane. The Cu-BTC@PVA/PVDF Janus membrane showed a rougher surface with an in-air water contact angle of 27.4˚ and an underwater oil contact angle of 152.8°. The Cu-BTC had minimal impact on mass transfer efficiency in MD process, and the Janus membrane exhibited excellent anti-oil-fouling and anti-NOM-fouling properties. The formation of the hydration layer, the slip boundary effect, and the electrostatic repulsion by the hydrophilic serrated interface were the main antifouling mechanisms. The hydrophobic-hydrophobic interaction was the main fouling mechanism of PVDF membrane for both oil and NOM. Sodium alginate (SA) displayed severe fouling with a compacted fouling layer in PVDF membrane due to the concentration polarization (CP) and gel layer formation. Inorganic fouling was the predominant fouling for the high CP and inorganic–organic coupling. While humic acid (HA) surpassed SA in Cu-BTC@PVA/PVDF Janus membrane for the stronger hydrogen bond, hydrophobic-hydrophobic interaction was significantly alleviated. Inorganic fouling was also significantly alleviated due to the strong electrostatic repulsion effect. The prepared Janus membrane has great potential to promote MD dealing with hypersaline industrial wastewaters containing complex organic matters.
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2024
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IF 4.9
Ke Li,Qifei Xia,Lei Jin,Rongbin Xu,Yi Zhong,Daquan Yu
Leveler additives for Cu electrodeposition are critical for achieving bottom-up filling in micrometer scale and high aspect ratio (AR) through-silicon vias (TSVs). This study explores a highly effective imidazolium-based leveler electroplating formulation, which successfully achieves void-free filling of TSVs with a diameter of 3 μm and a depth of 45 μm (with an ultra-high AR of 15:1). Molecular dynamics simulations reveal that the leveler, 1,2-dimethyl-3-propylimidazolium iodide (DMPII), demonstrates a strong adsorption effect on the Cu surface. Electrochemical tests show that DMPII enhances the inhibitory effect of polyethylene glycol (PEG) while simultaneously amplifying the accelerating effect of bis-(sodium sulfopropyl)-disulfide (SPS). The complex interplay among these additives ultimately leads to a significant inhibitory effect on the electrochemical reduction of Cu ions at the TSV sidewalls, while promoting deposition at the bottom of the TSV. Furthermore, minimal impurities are detected in the electroplated Cu layer. These findings suggest that this DMPII-based electroplating formulation holds significant promise for the fabrication of ultra-high AR TSVs to enable future high-density 3D integration.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Ziyi Li,Jia Xiong,Yufei Huang,Yangqiang Huang,Geoffrey I.N. Waterhouse,Ziyun Wang,Yu Mao,Zhiwu Liang,Xiao Luo
Photocatalytic CO 2 reduction reaction (CO 2 RR) is usually constrained by sluggish kinetics and low product selectivity. Herein, a Cu-doping multi-tier hierarchical S-scheme heterostructure Cu-ZnIn 2 S 4 /ZIF-67 was fabricated, achieving highly efficient photocatalytic CO 2 RR under visible light without additional thermal input. At low pressure (absolute pressure 40 kPa), the optimized catalyst 2Cu-ZISF demonstrated a CH 4 yield of 22.27 μmol g −1 h −1 with a selectivity of 94.7 %. In situ XPS and EPR confirmed that the photogenerated charge transfer obeys an S-scheme mechanism, with Cu sites serving as electron-rich centers, facilitating spatial charge separation. In situ DRIFT detected reaction intermediates of photocatalytic CO 2 RR mechanism, and Gibbs free energy calculations via Density Functional Theory revealed that Cu incorporation significantly stabilizes surface CO* species, thus reducing CO(g) production and facilitating hydrogenation, thereby acting as targeted active sites for CH 4 production. This work overcomes the limitations of slow reaction kinetics and offers an in-depth understanding of how to design effective S-scheme heterojunction photocatalysts and their charge transfer mechanisms.
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Molecular Catalysis
·
2025
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IF 4.9
Haoyu Jia,Jinyue Hu,Le Zhao,Xiaoke Zheng,Weisheng Feng
Baohuoside I, a valuable flavonoid derivative of Herba Epimedii , exhibits superior bioactivities compared to its precursor, icariin. The conversion of icariin to baohuoside I using β-glucosidase (β-G) is an efficient approach for industrial production. Herein, β-G was successfully immobilized into a porous materials metal-organic frameworks (MOFs) via a simple one-pot coprecipitation method. The β-G@MOF biocomposite exhibited high encapsulation efficiency and excellent tolerance to extreme pH, high temperature, organic solvent and glucose. Remarkably, β-G@MOF retained its full initial activity even at 200 mM glucose. The β-G@MOF has a lower K m value compared with the free β-G, indicating enhanced substrate affinity. A conversion of 99.8 % was achieved in the hydrolysis of icariin to baohuoside I within 2 h. Additionally, β-G@MOF exhibited significantly reusability, maintaining 70.5 % yield after eight cycles at 60 °C. This study provides a simple, efficient, and sustainable approach for industrial production of baohuoside I and has potential for hydrolyzing other poorly soluble flavonoids.
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Materials Today Chemistry
·
2025
·
IF 6.7
Liuqin Zhang,Huali Li,Gege Zhang,Qiuping Li,Fa-Qian Liu
Marine biofouling can cause economic, environmental and safety issues. Here the Cu-MOF/SiO 2 aerogel@PDMS coatings were prepared to prevent the colonization of fouling organisms. The Cu-MOF-74 which can continuously provide copper ions was successfully synthesized through a simple method. SiO 2 aerogel was employed to immobilize Cu ions (Cu-MOF) by the formation of - Si - O -Cu- O -, thereby achieving the goal of more stable release of copper ions from the coating. And the improvement of coating hydrophobicity also helps to enhance the stability of MOFs. The Cu-MOF/SiO 2 aerogel@PDMS coating exhibits significant long-term antibacterial performance, with a maximum antibacterial rate of 99.5 %. And it can enhanced the long-term static anti-biofouling performance of PDMS in the local sea by effectively preventing the colonization of macrofouling organisms (e.g. barnacles, calcareous tubeworms).
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Applied Materials Today
·
2024
·
IF 7.2
Yuan Gao,Lian-Peng Li,Si-Yan Gong,Jia-Hui Huang,Shuo Xiang,Gan He,Qiong-Yu Wang,Mian Hu,Junliang Wang,Zhiyan Pan,Zhong-Ting Hu
Neonicotinoids as one of the newest major class of insecticides is a kind of persistent pollutants. Herein, copper-substituted zinc ferrites (Cu 0.75 Zn 0.25 Fe 2 O 4 ) prepared in subcritical aqueous solution has a nanosize of ∼2 nm with high crystallinity and strong magnetic property. At low catalyst dosage of 0.05 g L −1 , peroxymonosulfate (PMS) can be effectively converted into sulfate radicals in Cu 0.75 Zn 0.25 Fe 2 O 4 /PMS system. Thiamethoxam (THIA) degradation rate is in the order of Cu 0.75 Zn 0.25 Fe 2 O 4 > CuFe 2 O 4 > ZnFe 2 O 4 (124, 84, 21 × 10 −3 min −1 , respectively). At pH ∼7.0, THIA degradation efficiency can be over 99 % in 40 min. The radical species ( e.g. , HO • , SO 4 •− and 1 O 2 ) were demonstrated by EPR spectra using probe molecules. The majority effects in Cu 0.75 Zn 0.25 Fe 2 O 4 /PMS system with kinetics modelling were comprehensively investigated as well. This work provides that multi-metal coupling, i.e. , Cu(Ⅰ)/Cu(Ⅱ) & Fe(Ⅱ)/Fe(Ⅲ), in spinel structure by polyhedral design is an effective strategy for enhancing the catalytic activity. The Cu 0.75 Zn 0.25 Fe 2 O 4 /PMS system has promising for water treatment of neonicotinoid insecticide with ease of recycling catalysts by magnetic separation.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Chen Wang,Congbi Li,Xiaohui Wu,Xiangling Zhang,Mingjie Huang,Tao Zhou
Efficient and sustainable generation of high-valent metal-oxo species (HVMs) is critical for selective decontamination via Fenton-like catalysis, however, maintaining electron density balance at the active sites remains challenging. In this study, a zeolite-supported CuO catalyst was found to induce complete and selective Cu(III) oxidation of organics through persulfate (PDS) activation. PDS activation and pollutant oxidation occurred simultaneously at the electron-rich ≡Cu sites and electron-deficient ≡Al centers, respectively. Notably, zeolite could successfully serve as an electron buffer by creating dual active centers with distinct electron densities, stabilizing the generation and retention of ≡Cu(III) for exceptional anti-interference capacity. Strong metal-support interactions tuned the ≡Cu d-band center closer to the Fermi level, efficiently promoting electron transfer to ≡Cu sites through the Al/Si-O-Cu bond for the formation of ≡Cu(III). This study unveils a zeolite-based electron buffering strategy and presents an advanced approach for developing highly efficient catalysts in PDS activation and HVMs-mediated water purification.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Shuting Liu,Ziyu Zengcai,Jingyao Yang,Tianhao Wang,Wenting Lin,Yunhong Pi,Tiejun Wang
To achieve highly efficient in situ hydrogen release from methanol/water reforming at lower temperature, integrating solar-energy provides a promising strategy to activate methanol/water while significantly reducing the activation energy. Herein, we report a series of novel MOF-based photothermal catalysts, mUiO-67-bpy-CuX, featuring enhanced H 2 O affinity and spatially isolated Cu-pyridine active sites for photothermal-driven reforming process of methanol solutions (PTRM). These catalysts exhibit distinct active sites that separately adsorb and activate H 2 O and CH 3 OH, with synergistically photothermal effect leading to an exceptional H 2 evolution activity of 121.1 mmol‧g cat −1 ‧h −1 within 80 min at 210 ℃ and an overall turnover number (TON) of 25904 over 68 hours without significant deactivation, with a high apparent quantum efficiency (AQE) of 54 %. Notably, the activation energy is reduced by 44 % compared to thermal-only systems, and the H 2 production is initiated even at 100 °C. The photothermal H 2 evolution activities of mUiO-67-bpy-CuX correlate with the lability of X counteranions, suggesting open coordination environments of Cu sites generated by labile X groups facilitate Cu + -N intermediate formation upon photoexcitation. Additionally, the Zr 6 nodes and increased mesoporosity in the modulated MOF enhance H 2 O adsorption and dissociation at low temperatures, promoting OH‧ generation. While Cu + -N interfaces are responsible for effective cleavage of the C-H bonds in CH 3 OH. This work highlights the design of MOF-based photothermal catalyst with isolated metal sites for enhanced H 2 production from CH 3 OH/H 2 O reforming at low temperatures.
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