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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

MOF-derived low Ru-loaded high entropy alloy as an efficient and durable self-supporting electrode in rechargeable liquid/flexible Zn-air batteries

Zunpeng Hu,Qian Geng,Senjie Dong,Minghui Wang,Yuqian Song,Wenjing Sun,Han Diao,Ding Yuan

Exploiting the high-entropy alloy (HEA) electrocatalysts with the synergistic effect of multi-metal components is an effective approach to address the slow kinetics and undesirable stability of the oxygen evolution reaction (OER) in Zn-air batteries (ZABs), but still faces many challenges. In this study, a multimetallic Metal-organic framework (MOF)-derived HEA catalyst was successfully fabricated on carbon fiber as a flexible self-supporting electrode (denoted as CC@FeCoNiMoRu-HEA/C) for high-performance liquid/flexible ZABs using a facile and cost-effective strategy. The three-dimensional (3D) highly open network framework and hierarchical porous structure accelerate the mass transport of OH − /O 2 and charge transfer. The electronic structure adjustment, lattice defects and high entropy effects enable the CC@FeCoNiMoRu-HEA/C catalysts to perform high OER catalytic activity and strong durability while reducing the Ru content and lowering the economic cost. In situ Raman spectra and XPS results reveal the generation of metal-OOH intermediates on the HEA surface during the OER process. In a practical demonstration, the liquid ZAB assembled with CC@FeCoNiMoRu-HEA/C + Pt/C as the air electrode offers stable open-circuit voltage, large power density, excellent specific capacity and satisfactory cycle life, outperforming the commercial RuO 2  + Pt/C-based reference ZAB. More attractively, the flexible solid-state ZAB also achieves fast dynamic response, high peak power density, robust cycling stability as well as favorable mechanical flexibility, indicating a promising application prospect in future flexible electronics and wearable devices. This work provides a viable pathway to develop low precious metal-loaded HEAs as advanced OER self-supporting electrocatalysts and realize high-performance flexible energy storage devices.

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CARBON · 2025 · IF 11.6

Organic lactam induces the secondary recrystallization of zeolite β to form hierarchical porous carbon nanocages for efficient oxygen reduction and Zn-air batteries

Hao Liu,Guangwu Yang,Fuqiang Duan,Xiaoli Qiu,Guangrun Ren,Tingting Zhang,Jinshi Yu,Yanli Chen

In this study, we present a novel synthesis of hierarchical carbon nanocages (HCNC) with diverse pore structures tailored for efficient oxygen reduction reactions (ORR) and advanced performance in zinc-air batteries (ZABs). The hierarchical structure was achieved using a dissolution-recrystallization strategy, where N, N-dimethylpyrrolidone was employed to activate the zeolite β framework. The resultant hierarchical β-zeolite nanocage (HβNC) was subsequently used as a template for synthesizing the HCNC via chemical vapor deposition. The HCNC exhibited a multilevel porous structure, including micropores, mesopores, and macropores, optimizing mass transfer and providing high surface area for active site exposure. By introducing Fe-Nx active sites through an impregnation-pyrolysis method, the Fe–N/HCNC catalyst was synthesized and tested for ORR. The catalyst demonstrated superior activity, stability, and corrosion resistance, outperforming commercial Pt/C catalysts with a half-wave potential of 0.905 V. Additionally, the Fe–N/HCNC-based ZAB displayed excellent electrochemical performance, high power density, and enhanced durability. The This work not only provides a novel approach to carbon nanocage synthesis, and the unique structural characteristics of HCNC offer promising opportunities in energy storage and conversion technologies, addressing limitations in catalyst stability and mass transport.

CAS / MDL: 7631-86-9 77-98-5
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Oxygen vacancy-mediated activation of Zn-O bonds at the S-scheme heterostructure interface for efficient uranium collection and resistance to biological contamination

Yachao Xu,Zhong Zhou,Peng Yu,Huiquan Gu,Zixu Zhang,Ying Wang

Efficient reduction of U(VI) to U(IV) during seawater uranium extraction remains a challenge. Here, cerium dioxide quantum dots were bonded to the surface of indium zinc sulfide (ZIS) to form ZIS composite cerium dioxide quantum dots (ZIS/QDs-Ce). The oxygen vacancies are able to activate the Zn-O bonds at the ZIS and QDs-Ce interfaces, thus enabling the constructed S-scheme heterojunction to show great potential in facilitating the separation and transfer of photogenerated carriers. ZIS/QDs-Ce exhibited high anti-bio-pollution activity by generating biotoxic free radical reactive oxygen species (ROS). The photo-induced reduction of uranium by ZIS/QDs-Ce in 10 ppm uranium spiked simulated seawater reached 99.6 %. Oxygen vacancies cause distortions in the crystal field, and the Zn-O bond activation process triggers the movement of ZIS/QDs-Ce from the singlet low-spin state to the stable triplet state, resulting in free-carrier trapping centers and optimized electronic energy band structures. ZIS/QD-Ce has superior uranium extraction capabilities and is highly recommended for uranium extraction from seawater.

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JOURNAL OF COORDINATION CHEMISTRY · 2018 · IF 1.703

Spacers-directed structural diversity of Co(II)/Zn(II) complexes based on S-/O-bridged dipyridylamides: electrochemical, fluorescent recognition behavior and photocatalytic properties

Guo-Cheng Liu,Yan Li,Ying Xiong,Xiang-Xiang Liu,Qiao-Min Li,Ju-Wen Zhang,Hong-Yan Lin,Xiao-Wu Li

To investigate the effect of the spacers of S-/O-bridged dipyridylamides on the structures of Co(II)/Zn(II) complexes, [Co(L1)(chda)]·1.5H2O (CP1), [Co(L2)(chda)] (CP2), [Zn(L1)(hip)]·DMA·2H2O (CP3), and [Zn(L2)(hip)]·2.8H2O (CP4) [L1 = N,N′-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide, H2chda = trans-1,4-cyclohexanedicarboxylic acid, L2 = N,N′-bis(pyridine-3-yl)-4,4′-oxybis(benzoic) dicarboxamide, H2hip = 5-hydroxyisophthalic acid, DMA = N,N-dimethylacetamide], have been solvothermally synthesized. X-ray single-crystal diffraction shows that CP1 is a 2-D 3,5-connected network based on Co-L1 linear chains and (Co-chda)2 double chains. CP2 features a 1-D structure derived from 1-D wave-like (Co-chda)2 double chains decorated by terminal L2 ligands. CP3 and CP4 show wave-like (4,4) networks constructed by 1-D Zn-L1 zigzag and Zn-hip zigzag (for CP3)/linear (for CP4) chains. The effect of the spacers of S-/O-bridged dipyridylamides on the structures of the title complexes was discussed. Electrochemical behaviors of CP1–CP2 and solid-state luminescent properties of CP3–CP4 were studied. The luminescence investigations show that CP3 and CP4 are recycled fluorescent probes for environmentally relevant Fe3+ ions. The photocatalytic properties for the degradation of methylene blue (MB) under ultraviolet light irradiation of CP3–CP4 and the recyclable materials after fluorescent sensing Fe3+ ions (named CP3@Fe3+ and CP4@Fe3+) have also been investigated.

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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Composition design, thermodynamic calculation and synthesis of rocksalt structure Mg–Co–Ni–Cu–Zn–O HEOs based on cluster-plus-glue-atom model

Jianjian Wang,Yue Yu,Zhiqiang Li,Hualin Wang,Shimin Liu,Tingting Yao,Weiwei Jiang,Nan Wang,Chaoqian Liu,Wanyu Ding,Zhihua Zhang,Chuang Dong

Multi-component high entropy oxides (HEOs) have attracted enormous attention due to their unique structures and potential applications. The conventional selection strategy to obtain HEOs is to search for equimolar cationic systems to maximize configurational entropy and avoid phase separation. We previously explored non-equimolar cationic rocksalt structure Mg–Co–Ni–Cu–Zn–O HEOs using cluster-plus-glue-atom model. In this paper, the mixing entropy, enthalpy and Gibbs free energy of constructed superclusters were numerically calculated and compared with the correlated crystal structure based on recent studies. It indicated the Gibbs free energy rather than mixing entropy agrees well with the phase stability of HEOs. Mg 28 Co 17 Ni 19 Cu 16 Zn 16 O 96 shows the optimal phase stability which is related to the lowest Gibbs free energy, reflecting a regular octahedral environment preferred by the cation composition in the system. Enthalpy and entropy are among important design criteria in determining the phase stability of HEOs but the function of enthalpy is obviously higher than that of entropy. This study provides a comprehensive way to access HEOs which is undoubtedly very important for the development of other non-equimolar cationic high entropy materials such as carbides , silicides , borides or nitrides .

CAS / MDL: 1309-48-4
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Efficient and selective adsorption of Ni(II) and Mo(VI) utilizing novel materials derived from in situ aminated Co/Zn-ZIF-Modified biochar

Feiyu Gao,Chaowen Tan,Yang You,Yong Hou,Hongyan Yan,Xuewei Lv,Jie Dang

The imperative need for efficient and selective adsorption of Ni(II) and Mo(VI) is crucial for resource utilization and environmental protection. However, this process faces a challenge due to the scarcity of adsorbents that can adeptly adsorb both metal ions simultaneously. To address this, this study introduces a novel composite adsorbent material, denoted as BECZN, achieved through composite cross-linking of waste orange peel biochar with in situ aminated cobalt/zinc-zeolitic imidazolate frameworks (Co/Zn-ZIF-NH 2 ). The incorporation of Co/Zn-ZIF-NH 2 enhances the availability of active groups within BECZN. The aerogel structure of BECZN prevents ZIF material collapse and agglomeration, thereby improving active site exposure. BECZN exhibits notable adsorption capacities, reaching 151.84 mg/g for Ni(II) at pH = 7 and 842.54 mg/g for Mo(VI) at pH = 3. Further investigations indicated that the adsorption of Ni(II) and Mo(VI) obeys the Langmuir isotherm model, while exhibiting pseudo-second-order kinetics and intraparticle diffusion characteristics. Notably, BECZN selectively adsorbs Ni(II) and Mo(VI) efficiently under acidic and neutral conditions, respectively. It can maintain high capacity under the interference of various cations and anions. Meanwhile, this excellent selective adsorption of Ni(II) and Mo(VI) by Co/Zn-ZIF-NH 2 is revealed at the atomic level using density functional theory (DFT) calculations. This study offers a theoretical basis and experimental reference for the design and synthesis of ZIF and biomass-based composite adsorbents.

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JOURNAL OF POWER SOURCES · 2024 · IF 8.1

Cu, Zn Co-doped ruddlesden-popper La1·2Sr0·8NiO4+δ oxides as high-performance air electrodes of medium-temperature protonic ceramic electrolysis cells

Zhengfeng Wang,Xiaoyun Miao,Xingzhi Zhu,Shihang Guo,Donglin Han,Xiaofeng Ye,Zhaoyin Wen

The Ln 2 NiO 4+δ compound (Ln = La, Pr, Nd) finds extensive use as a cobalt-free oxygen electrode material in protonic ceramic electrolysis cells (PCECs) owing to its unique RP-type structure and remarkable catalytic activity . In this study, Cu and Zn co-substitution is employed to fabricate a series of materials, within the La 1 · 2 Sr 0 · 8 Ni 0.5 Cu x Zn 0.5-x O 4+δ system (x = 0.1, 0.2, 0.3, 0.4, denote as LSNCZ14, LSNCZ23, LSNCZ32, and LSNCZ41), and the crystal structure, conductivity, proton absorption and electrochemical properties are comprehensively investigated. The LSNCZ41 exhibits the lowest polarization resistance of 0.83 Ω cm 2 at 600 °C in the symmetric cell. The PCEC single cell incorporating the LSNCZ41 air electrode demonstrates a high electrolysis current density of 1.5 A cm −2 (1.3 V) at 600 °C under 60 % humidity in air, furthermore, negligible degradation is observed under this high current density during electrolysis for over 250 h. These results indicate that LSNCZ41 possesses a higher concentration of interstitial oxygen ions and superior proton absorption capacity , significantly expediting the oxygen reduction reaction (ORR) and ionic transport processes. This material can be considered as a promising candidate for the PCEC air electrodes due to its superior stability in air with high steam content.

CAS / MDL: 13478-00-7
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RSC Advances · 2024 ·Vol. 14 ·期 46 ·34372-34380 · IF 3.9

Efficient synthesis of polycarbonate ether polyol via copolymerization of CO2 and 1,2-butylene oxide over a layered Zn–Co double metal cyanide catalyst

Chen Liu,Yan Cao,Xianqiang Zeng,Zheng Zheng,Ziqiang Han,Peng He,Liguo Wang

Polycarbonate ether polyol synthesized by the copolymerization of carbon dioxide (CO2) and epoxides is a promising technology for chemically fixing CO2 and manufacturing degradable polymeric materials. However, research on the copolymerization of CO2 and 1,2-butylene oxide (BO) to produce polycarbonate ether polyol is relatively scarce. Herein, we employed layered Zn–Co double metal cyanide (L-DMC) as a catalyst for the copolymerization of CO2 and BO to obtain polycarbonate ether polyol. Under optimized conditions, the L-DMC-mediated copolymerization of CO2 and BO displays excellent activity (catalytic productivity up to 1500 g polymer per g catalyst) and a high CO2 incorporation fraction in polycarbonate ether polyol rate of 35.5%. In situ FTIR spectroscopy experiments showed a short induction period (10 min) in polymerization and competition between the synthesized polycarbonate ether polyol and butylene carbonate (BC). The properties of easy preparation, stability, and excellent catalytic performance of L-DMC suggest that it may be a promising candidate for large-scale production of CO2–BO-based polymers.

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INORGANIC CHEMISTRY · 2024 · IF 4.3

Architecting N-doped Carbon Nanotube-Rich Carbon Nanofibers with Biomimetic Vine-Leaf-Whisker Structure as Robust Bifunctional Electrocatalysts for Rechargeable Zn–Air Batteries

Minghui Wang,Zihao Chen,Yuqian Song,Zunpeng Hu,Hanzhe Song,Senjie Dong,Ding Yuan

Efficient and durable bifunctional catalysts toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are urgently desirable but challenging for rechargeable Zn–air batteries (ZABs), especially flexible wearable ZABs. Inspired by the vine-leaf-whisker structure in nature, we proposed a three-dimensional (3D) hierarchical bifunctional catalyst (denoted as Co–Fe–Zn@N-CNT/CNF) consisting of N-doped carbon nanotubes embedded with abundant CoFe alloy nanoparticles, leaf-shaped N-doped carbon nanoflakes, and porous carbon fibers for rechargeable ZABs. The special biomimetic structure provides a large specific surface area, allowing for high exposure of the active site and ensuring fast mass transport/charge transfer. The close combination of CoFe bimetallic alloys and N-doped carbon nanotubes delivers high electrocatalytic activity, while the coexistence of various active sites such as metal nanoparticles (NPs), metal-Nx, doped N species, and their synergistic interactions endows the catalysts with more active sites. As such, the Co–Fe–Zn@N-CNT/CNF catalyst achieves superior bifunctional catalytic activities for the ORR (a half-wave potential of 0.84 V) and the OER (an overpotential of 326 mV at 10 mA cm–2) in alkaline media, comparable to commercial Pt/C and RuO2. Remarkably, both aqueous and solid-state ZABs assembled with Co–Fe–Zn@N-CNT/CNF catalysts as air electrodes demonstrate excellent charging/discharging performance, high peak power density, and robust long-term cycling stability. More interestingly, the flexible ZAB performs well even under bending conditions, displaying satisfactory device stability and mechanical flexibility. This study presents a new collective morphological-composition-structural engineering strategy for exploiting the efficient bifunctional oxygen electrocatalysts, which is of great significance for high-performance rechargeable ZABs and wearable energy storage devices.

CAS / MDL: 693-98-1
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JOURNAL OF APPLIED POLYMER SCIENCE · 2024 · IF 2.7

Synergistic effect of Ca/Zn main stabilizer and maltitol auxiliary stabilizer on the thermal stability, mechanical properties, and transparency of poly(vinyl chloride)

Xuhui Wang,Guojie Zhang,Huanhuan Dong,Yong Zhang

Maltitol, a natural compound, offers a potentially eco-friendly alternative to conventional auxiliary thermal stabilizers. Its auxiliary stabilization effect was studied by discoloration tests, Congo red tests, thermogravimetric analysis, and UV–visible spectroscopy. Additionally, x-ray photoelectron spectroscopy and discoloration tests were used to study the stabilizing mechanisms of maltitol. Compared to dipentaerythritol, commonly used in the PVC industry, maltitol as an auxiliary stabilizer exhibits better improvement in thermal stability. This improvement is related to its melting point, ability to complex with zinc chloride, and content of hydroxyl groups. Furthermore, the addition of maltitol in PVC not only maintains good transparency of PVC basically unchanged but also improves the mechanical properties. Maltitol, as a natural, eco-friendly, and efficient auxiliary thermal stabilizer, exhibits a promising application prospect in PVC materials.

CAS / MDL: 6422-86-2
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Sr, Mn, and Zn extraction and separation from zinc electrolyte crystallization sediment with Ca and Sr sulfate cocrystallization structure: Reduction roasting reconstruction mechanism

Bingbing Liu,Yifei Zhang,Peidong Yang,Yanfang Huang,Yubin Xue,Hu Sun,Shuzhen Yang,Guihong Han

Zinc electrolyte crystallization sediment (ZECS) generated in the zinc hydrometallugy industry contains valuable metals of strontium (Sr), manganese (Mn), and zinc (Zn), which has economical value but poses potential detrimental to the environment. However, the extraction and recovery of Sr is extremely difficult due to the thermodynamically stable Ca and Sr sulfate cocrystallization structure in ZECS. The destruction of refractory sulfate cocrystallization structure is a prerequisite for Sr extraction, and the carbothermal reduction roasting method is demonstrated to be efficient for the phase reconstruction. In this study, a stepwise Sr, Mn, and Zn recovery process from ZECS via carbothermal reduction roasting-acid leaching-selective precipitation-multistage extraction was proposed. In the reduction roasting procedure, all the sulfates including CaSO 4 , SrSO 4 , and Ca 0.7 Sr 0.3 SO 4 are reduced to soluble sulfides. Meanwhile, most MnO 2 is converted to a low-valence Mn product (MnO) that is soluble in acid, and the reduced Zn (g) is volatilized which can be collected from the flue dust. In the acid leaching procedure, the leaching efficiencies of Sr, Ca, and Mn are as high as 97.34%, 97.44%, and 95.49% respectively, while 99.50% Si in the form of silica is enriched in the leaching residue. After that, high-purity Sr solution was obtained after selective precipitation for Mn removal and D2EHPA multistage extraction for Ca removal. 97.41% Mn in the leaching solution is precipitated by adjusting the pH value to 9.5 with NaOH solution. After four-stage extraction, 79.60% Sr and only 0.35% Ca are retained in the aqueous phase. The purified solution contains 2.88 g/L Sr, 0.052 g/L Ca, and 0.014 g/L Mn, which can be used to prepare industrial SrCO 3 product via the carbonation operation. Thermodynamic behavior and reduction roasting reconstruction mechanism of Ca and Sr sulfate cocrystallization structure in ZECS were discussed in this work. The distributions of main metal elements (Sr, Ca, Mn, and Zn) in ZECS during the carbothermal reduction roasting-acid leaching-selective precipitation-multistage extraction process were also systematically studied.

CAS / MDL: 7782-42-5 298-07-7
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JOURNAL OF POWER SOURCES · 2024 · IF 8.1

Stable and eco-friendly Ag–In–S/Zn–S quantum dots for an efficient and optically transparent luminescent solar concentrator-organic photovoltaic system

Kanglin Yu,Yuanyuan Xiao,Shiqi Hu,Xufan Zheng,Bowen Gao,Jingjing Xu,Zongzhe Li,Ruike Zhou,Yaowen Hu,Qingliang You,Biao Xiao,Renqiang Yang

Quantum dot (QD) based luminescent solar concentrator-organic photovoltaic (LSC-OPV) systems demonstrate significant potential in applications including building-integrated photovoltaics (BIPV). In this study, eco-friendly Ag–In–S/Zn–S QDs with a high photoluminescence quantum yield (PLQY = 73 %) are synthesized using a simple hydrothermal method. The influence of Zn-S precursor reactivity on QD properties is studied. The synthesized QDs exhibit excellent stability over a wide temperature range (90–360 K). The Ag–In–S/Zn–S LSCs maintain over 90 % of their initial PLQY after a two-month exposure to natural sunlight. Additionally, the power conversion efficiency (PCE) of the fabricated LSC-OPV system reaches 1.00 % under near-actual condition (9 mW cm −2 ). Moreover, when the irradiation intensity is further decreased to 0.4 mW cm −2 , the LSC-OPV system shows a PCE as high as 5.27 %, demonstrating that the LSC-OPV system can operate efficiently at low illumination intensities. Notably, the fabricated LSCs have minimal impact on the incident sunlight spectrum, making them suitable for BIPV applications. Thus, this study is a first that is known to report the integration of eco-friendly QD-based LSCs with organic photovoltaic cells, which positively contributes to the advancement of BIPV.

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