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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-11 · IF 16.6

Accelerating electrochemical CO2 reduction to multi-carbon products via asymmetric intermediate binding at confined nanointerfaces

Zhang Jin,Guo Chenxi,Fang Susu,Zhao Xiaotong,Li Le,Jiang Haoyang,Liu Zhaoyang,Fan Ziqi,Xu Weigao,Xiao Jianping,Zhong Miao

Electrochemical CO 2 reduction (CO 2 R) to ethylene and ethanol enables the long-term storage of renewable electricity in valuable multi-carbon (C 2+ ) chemicals. However, carbon–carbon (C–C) coupling, the rate-determining step in CO 2 R to C 2+ conversion, has low efficiency and poor stability, especially in acid conditions. Here we find that, through alloying strategies, neighbouring binary sites enable asymmetric CO binding energies to promote CO 2 -to-C 2+ electroreduction beyond the scaling-relation-determined activity limits on single-metal surfaces. We fabricate experimentally a series of Zn incorporated Cu catalysts that show increased asymmetric CO* binding and surface CO* coverage for fast C–C coupling and the consequent hydrogenation under electrochemical reduction conditions. Further optimization of the reaction environment at nanointerfaces suppresses hydrogen evolution and improves CO 2 utilization under acidic conditions. We achieve, as a result, a high 31 ± 2% single-pass CO 2 -to-C 2+ yield in a mild-acid pH 4 electrolyte with >80% single-pass CO 2 utilization efficiency. In a single CO 2 R flow cell electrolyzer, we realize a combined performance of 91 ± 2% C 2+ Faradaic efficiency with notable 73 ± 2% ethylene Faradaic efficiency, 31 ± 2% full-cell C 2+ energy efficiency, and 24 ± 1% single-pass CO 2 conversion at a commercially relevant current density of 150 mA cm −2 over 150 h.

CAS / MDL: 7440-50-8
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ACS Applied Energy Materials · 2023 · IF 6.4

Inducing High Power Factor in Cu2GeSe3-Based Bulk Materials via (Bi, Zn)-Co-doping

Zeqing Hu,Rong Wei,Chen Yan,Han Wan,Yu Liu,Longjiu Cheng,Zhou Li,Jiming Song

In this work, carrier concentration optimization and effective mass increase of Cu2GeSe3, which were considered to be a synergetic effect of electrical transport properties, were achieved by the co-doping of Bi and Zn on the Cu site. This effect led to a higher Seebeck coefficient of ∼307.76 μV K–1 at 723 K for the Cu1.988Bi0.01Zn0.002GeSe3 sample. This effect also resulted in a higher power factor of ∼8.66 μW cm–1 K–2 at 723 K and an average power factor of ∼6.29 μW cm–1 K–2 at the temperature range of 303–723 K for the Cu1.988Bi0.01Zn0.002GeSe3 sample, which were ∼135 and ∼196% larger than those of pristine Cu2GeSe3, respectively, and are among the highest value of the Cu2GeSe3-based sample. Benefiting from simultaneous optimization of the power factor, the maximum ZT of ∼0.75 for the Cu1.988Bi0.01Zn0.002GeSe3 sample at 723 K was obtained, which is ∼288% higher than that of Cu2GeSe3.

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Carbon Energy · 2023 ·Vol. 5 ·期 11 ·e343 · IF 20.5

Constructing an ion-oriented channel on a zinc electrode through surface engineering

Xin Liu,Kun Wang,Ying Liu,Fuhua Zhao,Jianjiang He,Hao Wu,Jianfei Wu,Han-Pu Liang,Changshui Huang

The inherent shortcomings of a zinc anode in aqueous zinc-ion batteries (ZIBs) such as zinc dendrites and side reactions severely limit their practical application. Herein, to address these issues, an ion-oriented transport channel constructed by graphdiyne (GDY) nanowalls is designed and grown in situ on the surface of a zinc electrode. The vertically stacked GDY nanowalls with a unique hierarchical porous structure and mechanical properties form a nanomesh-like interface on the zinc electrode, acting as an ion-oriented channel, which can efficiently confine the segmented growth of zinc metal in microscopic regions of hundreds of nanometers. In those microscopic regions, the uniform domain current density is effortlessly maintained compared with a large surface area, thereby inhibiting zinc dendrites effectively. Besides, due to the presence of the ion-oriented channel, the modified zinc anode demonstrates long-term stable zinc plating/stripping performance for more than 600 h at 1 mAh cm −2 in an aqueous electrolyte. In addition, full-cells coupled with MnO 2 show high specific capacity and power density, as well as excellent cycling stability with a capacity retention of 82% after 5000 cycles at 1 A g −1 . This work provides a feasible and accessible surface engineering approach to modify the electrode interface for confined and dendrite-free zinc deposition in aqueous ZIBs.

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ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY · 2023 · IF 6.8

Copper nanoparticles lead to reproductive dysfunction by affecting key enzymes of ovarian hormone synthesis and metabolism in female rats

Jie Luo,Mingzhi Zhang,Yang Deng,Haohuan Li,Qinglong Bu,Rui Liu,Jiansheng Yu,Shanshan Liu,Ze Zeng,Wei Sun,Ganbei Gui,Xicheng Qian,Yinglun Li

Studies on the general toxicity of copper nanoparticles (Cu NPs) have been conducted extensively, but their effects on reproductive toxicity remain unclear. In this study, we evaluated the toxic effect of Cu NPs on pregnant rats and their litter. The comparative in vivo toxicity of Cu ions, Cu NPs, and Cu microparticles (MPs) was studied in a 17-day repeated oral-dose experiment at the doses of 60, 120, and 180 mg/kg/day in pregnant rats. The pregnancy rate, mean live litter size, and number of dams decreased when exposed to Cu NPs. Moreover, Cu NPs caused a dose-dependent increase in ovarian Cu levels. The metabolomics results showed that Cu NPs caused reproductive dysfunction by altering sex hormones. In addition, in vivo and in vitro experiments showed that the ovarian cytochrome P450 enzymes (CYP450), responsible for hormone production, were significantly upregulated, whereas the enzymes responsible for hormone metabolism were significantly inhibited, resulting in a metabolic imbalance in some ovarian hormones. Furthermore, the results revealed that the nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) and mitogen-activated protein kinase (MAPK) signaling pathways significantly participated in the regulation of ovarian CYP enzyme expression. Overall, the results of the in vivo and in vitro toxicity experiments with Cu ions, Cu NPs, and Cu MPs suggested that toxicity from nanoscale Cu particles poses a more serious reproductive threat than microscale Cu as Cu NPs could directly damage the ovary and affect the metabolism of ovarian hormones.

CAS / MDL: 7440-50-8 10125-13-0
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OPTICAL MATERIALS · 2023 · IF 3.9

Transformation of carrier recombination mechanism as increasing the Germanium content in Cu2ZnGexSn1-xS4 single crystal prepared by molten salt method

Xupeng Zhu,Jun Zhang,Jun Liao,Qiang Ru,Wenfeng Fu,Zhiguo Wang,Shuwen Xue

Return to the physics origin of Cu 2 ZnSnS 4 type (CZTS-type, include CZGS, CZGTS, CZTSSe, etc.) material system, studying the influence of replacement elements on the optoelectronic properties by preparing high-quality single crystal materials to clarify the relationship between the key defect states of materials and carrier dynamics is the only way which must be passed to find efficient paths to improve the existing performance of CZTS-type optoelectronic devices. Herein, the optical behavior of high-quality Cu 2 ZnGe x Sn 1-x S 4 (CZGTS) single crystal prepared by the molten salt method and its relationship with Ge content were systematically studied using a photoluminescence (PL) and absorption tests at room temperature. Combined with the simple electrical tests, the transformation of carrier recombination mechanism as increasing the Germanium content in CZGTS single crystal before and after phase transition were reported for the first time. The transmission electron microscopy images, X-ray diffraction spectra and Raman scattering spectra of CZGTS were adopted to reveal the evolution mechanism of single crystal growth and phase transition caused by the change of Ge composition. The results show that the tunable blue-shift of PL peak emerges with the increase of Ge content and the excitation power dependence has a saturation phenomenon in the CZGTS single crystal particles. In consideration of the optical bandgap, PL peak position, PL intensity, carrier lifetime and the macroscopic resistivity, it is confirmed that the intrinsic PL behavior could be effectively tailored by different Ge amounts. Compared with the recombination PL of interband carrier (E p  > E g ) in Cu 2 ZnSnS 4 , the band tailed carriers (E p  < E g ) dominated by defect states would play a powerful role in CZGTS single crystal. Our work provides a strategy for tailoring the bandgap of CZGTS materials and a new perspective for understanding the influence of defect states on carrier dynamics.

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JOURNAL OF THE EUROPEAN CERAMIC SOCIETY · 2023 · IF 5.7

Effect of interfacial microstructure evolution on the peeling strength and fracture of silicon nitride/oxygen-free copper foil joints brazed with Ag-Cu-TiH2 filler

Liangliang Tang,Dongxu Yao,Yongfeng Xia,Hanqin Liang,Yu-Ping Zeng

Gas-pressure sintered silicon nitride (Si 3 N 4 ) ceramic was brazed to oxygen-free copper (OFC) foil using 20.22 ± 0.93 mg/cm 2 of Ag-Cu-TiH 2 filler at 875 ◦ C for 0.5 h. The effect of TiH 2 content on the 3D morphology, including the cross-section microstructure and etched surface morphology of Si 3 N 4 ceramic/OFC foil joints, was analyzed. An evolution model of the interfacial microstructure for joints was proposed based on 3D morphological analysis. The reaction between the brazing alloy and Si 3 N 4 ceramic formed the interfacial reaction layer and the inside reaction zones during brazing. The growth mechanism of the interfacial reaction layer was discussed in detail. The peeling test was used to evaluate the bonding strength of the Si 3 N 4 ceramic/OFC foil joints, and the optimum peeling strength of 25.1 N/mm was achieved at 5 wt% TiH 2 content. The interfacial microstructure of the joints changed with TiH 2 content, leading to different main fracture mechanisms and corresponding peeling strengths.

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JOURNAL OF MATERIALS SCIENCE · 2023 ·Vol. 58 ·期 13 ·5587-5598 · IF 4.5

Fabrication of recyclable magnetic Fe3O4–SiO2–Cu2O/Cu core–shell nano-catalyst for high-efficient reduction of aromatic nitro compound

Sun Shanshan,Zhang Zihao,Li Shuhan,Le Jinxun,Qian Haixia,Yin Xiaoshuang,Liu Ying,Yang Wenzhong,Chen Yun

Magnetic core–shell nanomaterial Fe 3 O 4 –SiO 2 –Cu 2 O/Cu was first successfully synthesized using an economical strategy. Using Fe 3 O 4 as a magnetic center for easy recycling and SiO 2 as the connecting layer, Cu elements were evenly and steadily distributed on the surface of the Fe 3 O 4 –SiO 2 –Cu 2 O/Cu core–shell nanostructure. The magnetic catalyst performed outstanding catalytic reduction activity for 4-nitrophenol (4-NP), and the complete catalytic reduction of 4-NP was achieved within only 5 min. What’s more, the catalyst could be well recycled, and the catalytic efficiency remained more than 90% after being reused 24 times. Graphical abstract

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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Defect engineering enabling p-type Mo(S,Se)2:TM (TM = V, Nb, Ta) towards high-efficiency kesterite solar cells

Junjie Fu,Afei Zhang,Dongxing Kou,Zewen Xiao,Wenhui Zhou,Zhengji Zhou,Shengjie Yuan,Yafang Qi,Zhi Zheng,Sixin Wu

One important issue limiting the development of Cu 2 ZnSn(S,Se) 4 (CZTSSe) solar cells is the severe recombination loss at CZTSSe/Mo(S,Se) 2 /Mo back contact, primarily arising from the non-matched potential barrier and inferior electric contact between absorber and weak n -type Mo(S,Se) 2 interfacial layer. It is expected that a p-type Mo(S,Se) 2 can effectively improve the hole extraction and enhance the device performance. In this work, we propose a plausible direction to build up an electrically benign back surface field by in-situ doping Mo(S,Se) 2 with group VB elements (TM = V, Nb and Ta). It is turned out that the generated V Mo , Nb Mo , or Ta Mo shallow acceptors could convert Mo(S,Se) 2 from weak n -type to p-type conductivity and increase its work function ( W F ) and hole concentration. With the contact of p-type absorber ( W F,absorber  <  W F,Mo(S,Se)₂ ), a benign ohmic contact with favorable downward band bending is formed, thereby accelerating the holes extraction and minimizing interface recombination loss. With significant gains in open-circuit voltage ( V oc ) and fill factor (FF), the Mo(S,Se) 2 :Ta device finally increases the efficiency from 10.82 % to 12.72 %. This convenient in-situ Mo(S,Se) 2 doping strategy is different from previous complicated or unstable cases and should serve as a basis for high-quality back contact engineering in kesterite photovoltaics.

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ChemistryOpen · 2019 ·Vol. 8 ·期 1 ·58-63 · IF 2.205

Manufacturing Graphene-Encapsulated Copper Particles by Chemical Vapor Deposition in a Cold Wall Reactor

Shujing Chen,Abdelhafid Zehri,Qianlong Wang,Guangjie Yuan,Xiaohua Liu,Nan Wang,Johan Liu

Graphical Steady as she goes : Graphene-encapsulated Cu nanoparticles (GCPs) fabricated by chemical vapor deposition in a cold wall reactor not only exhibited an outstanding thermal stability up to 179 °C, but also display an excellent thermal conductive performance in a thermally conductive adhesive (TCA). Functional fillers, such as Ag, are commonly employed for effectively improving the thermal or electrical conductivity in polymer composites. However, a disadvantage of such a strategy is that the cost and performance cannot be balanced simultaneously. Therefore, the drive to find a material with both a cost efficient fabrication process and excellent performance attracts intense research interest. In this work, inspired by the core–shell structure, we developed a facile manufacturing method to prepare graphene-encapsulated Cu nanoparticles (GCPs) through utilizing an improved chemical vapor deposition (CVD) system with a cold wall reactor. The obtained GCPs could retain their spherical shape and exhibited an outstanding thermal stability up to 179 °C. Owing to the superior thermal conductivity of graphene and excellent oxidation resistance of GCPs, the produced GCPs are practically used in a thermally conductive adhesive (TCA), which commonly consists of Ag as the functional filler. Measurement shows a substantial 74.6 % improvement by partial replacement of Ag with GCPs.

CAS / MDL: 7440-50-8
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SOLID STATE SCIENCES · 2019 · IF 2.155

Effect of palladium addition on electrochemical hydrogen storage properties of Co0.9Cu0.1Si alloy

Jianxun Zhao,Xiangjun Zhou,Yalan Guo,Zhongmin Su,Heng Liu,Wanqiang Liu,Shang Gao

Co 0.9 Cu 0.1 Si alloy was fabricated via mechanical alloying technique. Different amount of palladium was doped into the Co 0.9 Cu 0.1 Si alloy by ball milling. The composite alloy combined the excellent electrocatalysis activity of Pd, exhibiting preferable electrochemical performance than the original alloy. The Co 0.9 Cu 0.1 Si + 5 wt% Pd composite showed a C max of 559.2 mAh/g, significantly higher than that for Co 0.9 Cu 0.1 Si (502.1 mAh/g). The cycle stability was also enhanced after Pd loading. Moreover, the effect of ball milling time on electrochemical performance for the composite alloy was also investigated. 5 wt% Pd was mixed with the Co 0.9 Cu 0.1 Si alloy at different ball milling time (0.5 h, 1 h, 2 h, 3 h and 5 h). The optimal discharge capacity, capacity retention and high-rate dischargeability were obtained under the ball milling time of 2 h. The studies on electrochemical reaction kinetics demonstrated that the addition of Pd could accelerate the charge-transfer, thus enhancing the electrochemical activity and reaction kinetics of the alloy. The results indicated that Pd loading was an effective way in enhancing the electrochemical performance of Co 0.9 Cu 0.1 Si alloy.

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JOURNAL OF DRUG DELIVERY SCIENCE AND TECHNOLOGY · 2019 · IF 2.606

Internalization and subcellular transport mechanisms of different curcumin loaded nanocarriers across Caco-2 cell model

Xia Yan,Shuqing Cao,Ying Li,Pei Xiao,Zipeng Huang,Haiyan Li,Yan Ma

Curcumin (Cur) and its nanomedicine were researched in Caco-2 cells to investigate the internalization and subcellular transport across Caco-2 cell monolayer membrane. Cur loaded polymer micelle (PM), nanoemulsion (NE) and liposome (Lipo) were prepared to explore the transport process incorporating endocytosis, intracellular trafficking and transcytosis in Caco-2 cells. Firstly, nanocarriers could contribute to the cellular uptake and improve the stability of Cur within the Caco-2 cells. The co-mediation of clathrin , lipid raft/caveolae and/or macropinocytosis were involved in the internalization of Cur nanopreparations, indicating the diversity and partial energy-dependency of the endocytosis. Secondly, the endocytosed nanocarriers with Cur successively transported from apical early endosome to late endosome with the extension of incubation time . Furthermore, the intracellular location of Cur nanomedicines in lysosome and endoplasmic reticulum (ER) were detected and illustrated the actual transport of Cur nanomedicine to lysosome and ER. Finally, nanocarriers could enhance the transcytosis of Cur, involving the energy-dependent patterns. Especially, Cur-PM exhibited more advantages in regulating and coordinating the entry and the exit of Cur. The study indicated that the coexistence of multiple transport pathways had the potency to promote nanocarriers transcytosis and provided a rational dosage design for oral Cur.

CAS / MDL: 7440-50-8 59-02-9
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CHEMISTRY-A EUROPEAN JOURNAL · 2019 ·Vol. 25 ·期 49 ·11486-11493 · IF 5.16

Facile Synthesis of Peapod-Like Cu3Ge/Ge@C as a High-Capacity and Long-Life Anode for Li-Ion Batteries

Xinyi Wang,Xijun Xu,Jun Liu,Zhengbo Liu,Jiadong Shen,Fangkun Li,Renzong Hu,Lichun Yang,Liuzhang Ouyang,Min Zhu

Graphical Nanocomposite anodes : Uniform peapod-like Cu 3 Ge/Ge@C composites are fabricated successfully through a facile dopamine-coating and annealing route (see figure). Owing to the homogeneous carbon encapsulation and the addition of the inactive alloying phase Cu 3 Ge, this Ge-based anode exhibits an excellent high specific capacity, outstanding cycle stability, and excellent rate performance for LIBs. As anode materials for high-performance Li-ion batteries, peapod-like Ge-based composites, including Ge, a Li-inactive conducting Cu 3 Ge, and a porous carbon matrix are synthesized simply by annealing CuGeO 3 @dopamine in a H 2 /Ar atmosphere. The introduction of the carbon layer and inactive alloying phase Cu 3 Ge not only enhances the electrical conductivity of the Ge anode, but also reduces the volume change of Ge during the cell cycle as a buffer. In particular, the anode of this peapod-like Cu 3 Ge/Ge@C shows an excellent long cycle life as well as outstanding capacity performance, with a discharge specific capacity up to 934 mA h g −1 after 500 cycles.

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