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Energy Storage Materials · 2026 · IF 19.3

Unlocking higher Li-ion conductivity in Zr-based chlorides without compromising the cost-effectiveness

Xiaodong Zhou,Lv Hu,Jingming Yao,Mingrui Yin,Hui Li,Fang Chen,Yanxin Wang,Jinzhu Wang,Jianyu Huang,Cheng Ma

Identifying solid electrolytes with both high Li-ion conductivity and competitive cost is a grand challenge for the pursuit of commercially viable all-solid-state lithium batteries. Without involving overly expensive raw materials, the cost-effective solid electrolytes reported so far may only achieve ionic conductivities of 0.5−2 mS cm −1 at 25 °C, and further improvement seems challenging. Here, we discover that, compared with the extensively utilized metal cations for solid-electrolyte modification, the barely involved non-metal cations with higher ionic potentials may enable faster Li-ion transport. Following this principle, we modify the cost-effective Zr-based chloride solid electrolytes with the highly abundant Si 4+ , whose ionic potential is around 1.5−5 times those of typical metal cations. The 0.6Li 4 SiO 4 -ZrCl 4 obtained this way reaches an ionic conductivity of 3.2 mS cm −1 at 25 °C, greatly exceeding the aforementioned 0.5−2 mS cm −1 range for the existing cost-effective solid electrolytes. Thanks to such improved ionic conductivity, the all-solid-state cells with the Ni-rich layered cathode achieved reversible areal discharge capacities above 10 mAh cm −2 at 25 °C.

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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2022 ·Vol. 23 ·期 24 ·16121 · IF 6.208

Zr-Based Metal−Organic Frameworks with Phosphoric Acids for the Photo-Oxidation of Sulfides

Zhenghua Zhao,Mingjie Liu,Kai Zhou,Hantao Gong,Yajing Shen,Zongbi Bao,Qiwei Yang,Qilong Ren,Zhiguo Zhang

Heterogeneous Brønsted acidic catalysts such as phosphoric acids are the conventional activators for organic transformations. However, the photocatalytic performance of these catalysts is still rarely explored. Herein, a novel Zr-based metal−organic frameworkZr-MOF-Pwith phosphoric acids as a heterogeneous photocatalyst has been fabricated, which shows high selectivity and reactivity towards the photo-oxidation of sulfides under white light illumination. A mechanism study indicates that the selective oxygenation of sulfides occurs with triplet oxygen rather than common reactive oxygen species (ROS). WhenZr-MOF-Pis irradiated, the hydroxyl group of phosphoric acid is converted into oxygen radical, which takes an electron from the sulfides, and then the activated substrates react with the triplet oxygen to form sulfoxides, avoiding the destruction of the catalysts and endowing the reaction with high substrate compatibility and fine recyclability.Keywords:metal−organic frameworks;phosphoric acid;photo-oxidation;oxygen radical

CAS / MDL: 150-78-7
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FUEL · 2022 · IF 8.035

Synergetic effect of Ce/Zr for ethanol synthesis from syngas over Rh-based catalyst

Caixia Zhu,Kaizhuang Xu,Yuan Fang,Qian Lv,Kun Jiang,Huibo Zhao,Yang Chen,Peng Wang,Hua Yang,Lizhi Wu,Yu Tang,Li Tan

The direct synthesis of ethanol from syngas is a promising way in the field of clean and efficient use of fossil fuel, but it still suffers from insufficient ethanol selectivity and understanding of active sites. In this work, the Rh-based catalyst with Ce as promoter and ZrO 2 as carrier exhibits excellent catalytic performance, showing the selectivity of ethanol toward 24.3 %. Moreover, the yield of methane decreases to 4.8 %, and the formation of CO 2 is inhibited to a certain degree by tuning the active sites. The carrier is changed by doping Ce into the ZrO 2 lattice, which assists to form the Rh δ+ active sites. The synergetic effect of Ce and Zr is important to influence the state of Rh species in the catalysts, leading to the differences in the CO hydrogenation process. On the other hand, the Rh δ+ active sites are also stabilized by promoted surface oxygen vacancies in the 2.0Rh5.0Ce-ZrO 2 catalyst. The high-activity catalyst with Rh δ+ active sites will be helpful to understand the real active sites of Rh-based catalysts for ethanol synthesis from syngas, thereby guiding further design of the related catalyst with high performance to meet the industrial demand in syngas converting to ethanol.

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COMPOSITES PART B-ENGINEERING · 2022 · IF 11.322

Enabling thermally enhanced vibration attenuation via biomimetic Zr–fumarate MOF-based shear thickening fluid

Shuai Liu,Xiwen Fan,Fang Yuan,Min Sang,Jianyu Zhou,Junshuo Zhang,Shouhu Xuan,Sheng Wang,Xinglong Gong

This work reported a biomimetic shear thickening fluid (STF) with thermally enhanced shear thickening effect for smart vibration attenuation system. It was developed by introducing Zr–fumarate metal-organic framework (MOF) crystals into a solvent mixture comprised of polyethylene glycol , polyacrylic acid and Ca 2+ , which endowed it with the cooperative effect of electrostatic and hydrophobic interactions . As the temperature raised from 25 to 35 °C, the STF containing 55 vol% MOF (STF-55) yielded a favorable shear thickening reinforcement with a notable viscosity growth of 1760-7953 Pa s. Besides, its storage modulus increased from 14 to 3036 Pa at 25–55 °C under a 0.1 Hz shear frequency, revealing a significant improvement in mechanical performance, as also demonstrated by transient shear rheological experiments. STF was incorporated into sandwich structures to improve the damping performance, with the natural frequency and damping ratio investigated at various ambient temperatures. Since the thermal enhanced viscosity could promote energy dissipation , the damping ratio of STF-55 filled sandwich structure obtained a substantial improvement from 0.85% to 1.93% at 25–55 °C. Thus, STF-55 based turbine blade and building damping pile were fabricated, which not only reduced the external vibration stimuli with average responsive accelerations of 7.3 and 0.8 m 2 s -1 , but also presented attenuated levels of 6.9 and 0.6 m 2 s -1 at increasing temperatures, respectively. In conclusion, this work provided guiding approach for highly adaptive vibration attenuation at high-temperature environment.

CAS / MDL: 10026-11-6 9003-01-4
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2022 · IF 5.518

Enhanced adsorption desulfurization performance of Cu+-exchanged UiO-66(Zr) with hierarchical porous structure

Konglu Guo,Yueyang Xu,Yan Yin,Yongping Zeng

Adsorption desulfurization can effectively remove thiophene-containing compounds in fuels. UiO-66 is a potential candidate for adsorption desulfurization due to the excellent chemical stability and resistances to acids and alkali. However, the adsorption capacity is relatively low for the big molecules of sulfide (such as thiophenes) because of the pore size in the microporous structure. We used Zn 4 O(BC) 6 as a template to synthesize a new π-complexation adsorbent (H-UiO-66-SO 3 Cu(I)) via ion-exchange and steam-induced reduction, with hierarchical porous (microporous and mesoporous) structure. The adsorbent was characterized by FT-IR, XRD , SEM , TEM and N 2 adsorption-desorption isotherms. The results show that H-UiO-66-SO 3 Cu(I) has the stable structural properties with the new mesopores . H-UiO-66-SO 3 Cu(I) has a good adsorption performance for thiophene and benzothiophene in the model fuel. The regeneration results show that H-UiO-66-SO 3 Cu(I) can be recycled four times and still has good adsorption performance.

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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

High-performance Hf/Ti-doped defective Zr-MOFs for cefoperazone adsorption: Behavior and mechanisms

Menghan Qin,Yumiao Shi,Dingkun Lu,Jingjing Deng,Guoyue Shi,Tianshu Zhou

Due to the excessive use, cephalosporin antibiotics have been detected in various aquatic environments, which may result in environmental and health concern. In this study, bimetallic metal–organic frameworks (MOFs), Hf-UiO-66 and Ti-UiO-66, were successfully designed and obtained via post-synthetic method from UiO-66 for the adsorption of cefoperazone. A serious of adsorption experiments were investigated. The adsorption kinetics and isotherms demonstrated that the adsorption process followed pseudo-second-order kinetic model and Langmuir isotherm model. Hf/Ti-UiO-66 exhibited much better adsorption performance than the undoped UiO-66. Particularly, Hf-UiO-66 had the highest adsorption capacity (346.0 mg g −1 ). With the introduction of Hf or Ti, the chemical coordination environment changed, which resulted in defective structures of MOFs. Such defective structures increased the adsorption active sites, changed the surface charges and enlarged pores. Based on the characterization by FT-IR, XPS, and zeta potential, it was identified that the electrostatic attraction, π-π stacking, hydrogen bonding and metal complexation were the driving force for the high adsorption capacity of the bimetallic MOFs. The as-prepared MOFs displayed good stability and reusability. This work provides a great prospect for the design and application of bimetallic defective MOFs in cephalosporins removal in environmental water.

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Catalysts · 2022 ·Vol. 12 ·期 8 ·901 · IF 4.501

An Efficient Zr-ZSM-5-st Solid Acid Catalyst for the Polyol Esterification Reaction

Huaigang Su,Ze Zong,Wenjing Lou,Qin Zhao,Xiaobo Wang,Xiang Feng,Yanxing Qi,Zhaoning Song

In this study, Zr active species were implanted into a ZSM-5 zeolite framework to form a solid acid catalyst through steam treatment and the liquid-solid isomorphous substitution process. The as-synthesized Zr-ZSM-5-st catalyst ensured excellent esterification of trimethylolpropane and fatty acids (FAs) to achieve a polyol ester production yield of 94.41%. Combined with N2physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, transmission electron microscopy mapping, X-ray photoelectron spectroscopy, NH3temperature-programmed desorption, and inductively coupled mass plasma spectroscopy were conducted. The results revealed that the excellent performance of Zr-ZSM-5-st catalyst could be attributed to the enhanced acidity and the developed surface area and pore structure.Keywords:Zr-containing solid acid catalyst;ZSM-5 zeolite;polyol ester;esterification;lubricating ester oils

CAS / MDL: 78-10-4 167114-91-2
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JOURNAL OF MATERIALS SCIENCE · 2021 ·Vol. 56 ·期 34 ·19060-19074 · IF 4.22

A novel electrochemical sensor via Zr-based metal organic framework–graphene for pesticide detection

Gao Nan,Tan Runan,Cai Zhiwei,Zhao Hui,Chang Gang,He Yunbin

Methyl parathion (MP), as a typical organophosphorus pesticide, has been widely used in pest control and plant growth regulation. Simultaneously, the problem of pesticide residues also poses a serious threat to the environment and human health. Currently, pesticide residue detection technology still faces great challenges in practical applications due to the problems of expensive facilities and complicated operations in conventional analysis methods. To address these problems, a novel nonenzymatic electrochemical pesticide sensor was reported. A zirconium-based metal organic framework material with terephthalic acid as a ligand (Zr-BDC) was designed to combine with electro-reduced graphene oxides (rGO). The Zr-BDC-rGO nanocomposite contains Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and a higher adsorption capacity for MP. Moreover, rGO has a high specific surface area and excellent electron transport capability, making it an excellent functionalized adsorption and substrate material, which could improve the conductivity of the material and achieve a lower detection limit. Upon optimization, this sensor provided a wide linear range from 0.001 to 3.0 μg mL −1 and low limit of detection 0.5 ng mL −1 for MP. This work provides a rapid, sensitive and cost-effective sensing platform for pesticide residue detection. Graphical abstract

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ACS Applied Nano Materials · 2021 · IF 5.097

Micropatterned Amorphous Zr-Based Alloys Coated with Silica Nanoparticles as Superhydrophobic Surfaces against Abrasion

Mingjie Li,Wenxin Luo,Haoyang Sun,Jingfu Xu,Kar Wei Ng,Xing Cheng

Superhydrophobic metallic surfaces with mechanical stability as well as self-cleaning and anticorrosion functions are highly desirable because of their promising applications in various aspects. Large apparent water contact angles (≥150°) on metal surfaces are usually realized by high surface roughness and low surface energy. However, rough nanoscale features and low-energy coatings are prone to wear, causing degradation of the local wetting property during service. Herein, we develop a low-cost and scalable fabrication methodology to prepare composite superhydrophobic surfaces (water contact angle ∼154.7± 2.3° and sliding angle ∼1.2 ± 0.2°) by integrating a micropatterned amorphous alloy frame with functionalized nanoparticles. Amorphous interconnected microwalls provide augmented resistance against abrasion, whereas spray-coated nanomaterials residing within the frame impart water repellency. Metallic surfaces can withstand abrasion against sandpaper for 40 m under a local pressure of 120 kPa, before losing their perfect superhydrophobic performances. The composite surfaces also maintain its water repellency after mechanical bending, knife scratching, water impact jetting, ultraviolet (UV) irradiation, and acid immersion. We envisage that the design strategies here provide a practical route to manufacture water-repellent surfaces with metallic glass in harsh nautical applications.

CAS / MDL: 83048-65-1
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ENVIRONMENTAL SCIENCE & TECHNOLOGY · 2021 · IF 9.028

Stable Zr-Based Metal–Organic Framework Nanoporous Membrane for Efficient Desalination of Hypersaline Water

Haotian Li,Mao Fu,Shi-Qiang Wang,Xiangyong Zheng,Min Zhao,Fenglin Yang,Chuyang Y. Tang,Yingchao Dong

Treatment of hypersaline waters is a critical environmental challenge. Pervaporation (PV) desalination is a promising technique to address this challenge, but current PV membranes still suffer from challenging issues such as low flux and insufficient stability. Herein, we propose in situ nanoseeding followed by a secondary growth strategy to fabricate a high-quality stable metal–organic framework (MOF) thin membrane (UiO-66) for high-performance pervaporation desalination of hypersaline waters. To address the issue of membrane quality, a TiO2 nano-interlayer was introduced on coarse mullite substrates to favor the growth of a UiO-66 nanoseed layer, on which a well-intergrown UiO-66 selective membrane layer with thickness as low as 1 μm was finally produced via subsequent secondary growth. The PV separation performance for hypersaline waters was systematically investigated at different salt concentrations, feed temperatures, and long-term operation in different extreme chemical environments. Besides having nearly complete rejection (99.9%), the UiO-66 membrane exhibited high flux (37.4 L·m–2·h–1) for hypersaline waters, outperforming current existing zeolite and MOF membranes. The membrane also demonstrated superior long-term operational stability under various harsh environments (hypersaline, hot, and acidic/alkaline feed water) and mild fouling behavior. The rational design proposed in this study is not only applicable for the development of a high-quality UiO-66 membrane enabling harsh hypersaline water treatment but can also be potentially extended to other next-generation nanoporous MOF membranes for more environmental applications.

CAS / MDL: 10026-11-6 100-21-0
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2021 ·Vol. 28 ·期 32 ·43815-43830 · IF 4.223

Electrocatalytic oxidation of ciprofloxacin by Co-Ce-Zr/γ-Al2O3 three-dimensional particle electrode

Liu Yaxin,Ma Yongwen,Wan Jinquan,Wang Yan,Sun Jian,Xue Yangyang

In this work, Co-Ce-Zr/γ-Al 2 O3 3 particle electrodes were prepared for the efficient degradation of ciprofloxacin (CIP). Co-Ce-Zr/γ-Al 2 O 3 particle electrodes were analyzed with a scanning electron microscope (SEM), X-Ray Diffraction (XRD), X-Ray Fluorescence Spectrometer (XRF), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray spectroscopy (EDS). According to the results, significant amounts of Co 3 O 4 , CeO 2 , and ZrO 2 were formed on the Co-Ce-Zr/γ-Al 2 O 3 particle electrodes. It was shown that when the conditions of the reaction system were at pH=6, conductivity of 4 ms/cm, current of 0.2 A, initial pollutant concentration of 100 mg/L, and material dosage of 15 g, CIP could be completely degraded within 40 min, and the energy consumed in the reaction was 41.3 kWh/kg CIP. The rate of total organic carbon (TOC) removal by Co-Ce-Zr/γ-Al 2 O 3 particle electrodes was recorded to be approximately 52.6%. Using a response surface methodology, we explored the optimal operating conditions. At the same time, we also explored the influence of inorganic anions in water and actual water medium on the rate of CIP removal. In addition, the ESR data proved that the main active substance in the reaction system was ·OH. The degradation intermediates were investigated, and the possible mechanism was proposed. Thus, this research provided a new solution for the treatment of antibiotic-containing wastewater.

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JOURNAL OF INORGANIC BIOCHEMISTRY · 2021 · IF 4.155

Zr-based acid-stable nucleotide coordination polymers: An excellent platform for acidophilic enzymes immobilization

Yucui Jiang,Saixing Liu,Qipeng Yuan,Hao Liang

Acidophilic enzymes play an important role in special industrial catalytic reactions. In this work, we reported Zr-based acid-stable nucleotide coordination polymers (CPs) for efficiently improving acidophilic enzymes immobilization . Among all tested metal ions , the Zr 4+ /AMP CPs exhibited the highest acid stability and enzyme affinity. As a typical acidophilic enzyme, the immobilized Chloroperoxidase by Zr 4+ /AMP CPs displayed robust reusability in the asymmetric synthesis of modafinil, remained 95.7% of conversion rate and 99.1% enantiomeric excess (e.e.) value. This work displayed a novel acid-stable bioorganic and inorganic hybrid nanomaterial for acidophilic enzymes immobilization.

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