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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Inkless printing and advanced dynamic information anti-counterfeiting via photochromic system based on solid-state Zr/Ti-MOF@WO3 heterojunctions

Bingbing Cui,Guodong Fu

Given that heterojunction engineering is an effective method for improving the separation efficiency of photoexcited electrons in WO 3 -based photochromic systems, a series of solid-state photochromic Zr/Ti-MOF@WO 3 heterojunctions prepared via a facile hydrothermal strategy, where Zr/Ti-MOF with photosensitivity and chemical stability was selected as template to load WO 3 . Zr/Ti-MOF@WO 3 heterojunctions were verified as nanoparticles filled with thin layer structure and WO 3 was diffused into the Zr/Ti-MOF planar. The appropriate conductive band energies facilitate the transport of photostimulated electrons from Zr/Ti-MOF to WO 3 , resulting in a fast photresponse in color changes (it only takes 1 s). In addition, a carrier for information storage and data dynamic encryption was developed on the basis of the photochromic Zr/Ti-MOF@WO 3 heterojunctions. This work presents a promising way to improve the electron/holes separation efficiency by constructing unique heterojunctions and further explore novel WO 3 -based photochromic systems and broaden their applications in rewritable media and data security.

研究领域: 材料科学 · 光学工程
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RSC Advances · 2020 ·Vol. 10 ·期 33 ·19149-19156 · IF 3.119

A built-in self-calibrating luminescence sensor based on RhB@Zr-MOF for detection of cations, nitro explosives and pesticides

Liu Yang,Yu-Long Liu,Cheng-Guo Liu,Ying Fu,Fei Ye

A RhB@Zr-MOF composite with dual-emission properties was successfully constructed, which comprises a zirconium-based metal–organic framework and the luminescent dye molecule, Rhodamine B (RhB), embedded via the encapsulation method. The fluorescence intensity ratio of the two emissions was found to be ca. 370 nm/590 nm for RhB@Zr-MOF. The fluorescence intensity values of the two emissions of RhB@Zr-MOF can also be affected by the structures of analytes containing different organic groups. Due to the existence of the dual-emission properties in RhB@Zr-MOF, the relative fluorescence intensity of the emission peaks was introduced as a detection index instead of absolute fluorescence intensity. RhB@Zr-MOF, which possesses the characteristics of a built-in self-calibrating fluorescence sensor, was investigated for detecting cations, nitroaromatics and pesticides. Aside from high sensitivity and selectivity, recyclability is the most important property for sensing pesticides. This work shows that RhB@Zr-MOF can maintain its stability after 5 cycles of detecting nitenpyram, with LOD of 0.2 μM. These results demonstrate that dye@MOFs with dual-emission properties can be employed as multifunctional fluorescence sensors for different types of analytes, and that RhB@Zr-MOF provides a new paradigm for analyte sensing.

研究领域: 材料科学 · 分析化学 · 环境科学
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CHEMICAL ENGINEERING JOURNAL · 2017 · IF 6.216

Catalytic conversion of furfural to methyl levulinate in a single-step route over Zr/SBA-15 in near-critical methanol

Hao Chen,Houhang Ruan,Xilei Lu,Jie Fu,Timothy Langrish,Xiuyang Lu

In the present study, an economic and environmentally friendly bi-functional catalyst, Zr-SBA-15, has been prepared to develop a single-step process for synthesis of methyl levulinate (MLA) directly from furfural (FAL) in near-critical methanol without added H 2 . The presence of Zr in SBA-15, the structure of the Zr-SBA-15 catalyst, and its physical properties have been determined by X-ray diffraction (XRD), N 2 adsorption and desorption (N 2 -BET) and transmission electron microscopy (TEM). The Zr-SBA-15 catalyst has high activity for the production of MLA and good reusability. A possible reaction pathway containing two possible reaction pathways during this single-step synthesis of MLA has been proposed: the FAL has been transformed to β-Methoxy-2-furanethanol (MFE) and 2-Furfuryl methyl ether first, which then have been converted to MLA, and the conversion of FAL to MFE has been much easier and faster than that to 2-FME, which may be the major reaction pathway. The SBA-15 has given high activity for the conversion of FAL to MFE, and the incorporation of Zr has converted the MFE to MLA efficiently. The reaction of FAL to MFE to MLA has been found to be the dominant reaction. Finally, the catalyst has shown good reusability for at least five times without any reduction in the catalytic activity.

CAS / MDL: 7789-75-5 59-30-3
研究领域: 催化化学 · 可再生化学
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CHEMICAL ENGINEERING SCIENCE · 2024 · IF 4.1

Influence of pore structure on catalytic performance of Cs-Zr/SiO2 catalyst for methyl methacrylate synthesis from methyl propionate and formaldehyde

Chenxi Feng,Junyang Liu,Kai Zhao,Lei Wang,Zengxi Li,Guoliang Zhang,Chunshan Li

Methyl methacrylate (MMA) synthesis via aldol condensation of methyl propionate with formaldehyde over Cs-based supported catalysts is intensively investigated, while the effect of their pore structures on catalytic performance still lacks in-depth understanding. Herein, series of Cs-Zr/SiO 2 catalysts with different pore structures were prepared for this aldol condensation. The physicochemical characteristics of as-prepared Cs-Zr/SiO 2 catalysts were characterized using physical N 2 adsorption–desorption isotherms and CO 2 -/NH 3 -TPD. In addition, the impact of pore structure on mass transfer, adsorption, and desorption of reactants and products was studied through in situ DRIFTS. The results show that the acid and base site densities elevated with the increasing pore volume. The mass transfer of reactants and products could be promoted with increasing pore size, while their adsorption energies exhibited a volcanic trend. As a result, the Cs-Zr/SiO 2 catalysts having average pore diameter of 12-18 nm and acid-base balance was considered as the optimal candidate for MMA production.

研究领域: 催化化学 · 材料科学
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

UiO-66(Zr)-2OH-Supported Pd0 NP Catalysts Accelerated a Fenton-Like Reaction: Iron Cycling and Hydrogen Peroxide Generation Achieved Simultaneously

Ying Gao,Qinqin Chen,Xinhao Shen,Shuang Yao,Zhiwen Jiang,Sanjian Ma,Hailiang Yang,Juanhong Li,Zixia Lin,Xin Liu

Both the sluggish kinetics of Fe(II) regeneration and usage restriction of H2O2 have severely hindered the scientific progress of the Fenton reaction toward practical applications. Herein, a reduction strategy of activated hydrogen, which was used to simultaneously generate H2O2 and accelerate the regeneration of ferrous in a Fenton-like reaction based on the reduction of activated hydrogen derived from H2, was proposed. Two types of composite catalysts, namely, Pd/UiO-66(Zr)-2OH and Pd@UiO-66(Zr)-2OH, were successfully prepared by loading nano-Pd particles onto the outer and inner pores of UiO-66(Zr)-2OH in different loading modes, respectively. They were used to enhance the reduction of activated hydrogen. The characterization results based on the analysis of scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy revealed that the materials were successfully prepared. By using a trace amount of ferrous iron and without adding H2O2, trimethoprim (C0 = 20 mg·L–1), as a target pollutant, could be nearly 100% degraded within 180 min in the reaction system composed of these two materials. The cycle of iron and the self-generation of H2O2 were verified by the detection of ferrous H2O2 in the system. Density functional theory calculation results further confirmed that the pore-filled Pd0 NPs, as the main catalytic site for Pd@UiO-66(Zr)-2OH, could produce H2O2 under the combined action of hydrogen and oxygen. The Pd@UiO-66(Zr)-2OH system had excellent stability after multiple applications (at least 6 cycles), all of which resulted in 100% removal of trimethoprim. The degradation efficiency of the Pd/UiO-66(Zr)-2OH system for TMP gradually decreased from 97 to 80% after six cycles. The results of electron paramagnetic resonance combined with classical radical burst experiments revealed the degradation pathways in the reaction system with hydroxyl radicals and singlet oxygen as the main reactive oxygen particles.

研究领域: 环境科学 · 催化化学
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Nano Energy · 2025 · IF 17.1

Modulating Cu-O-Zr interfaces on high-roughness MgO surface for reinforced hydrogen production from sorption-enhanced steam reforming of methanol

Zhao Sun,Huicai Wang,Xingxu Wang,Riguang Zhang,Zhiqiang Sun

Sorption-enhanced steam reforming of methanol (SE-SRM) offers a promising route for high-quality hydrogen production with in situ CO 2 capture; however, achieving an optimal balance between catalytic activity and CO 2 uptake capability, while ensuring catalyst stability, remains a significant challenge. In this study, a series of Zr-doped (0 wt%, 5 wt%, 15 wt%, 25 wt%) Cu-MgO catalytic sorbents are synthesized for SE-SRM. At 180℃, the hydrogen concentration and yield reach nearly 100 % and 10.35 μmol·g −1 ·s −1 . Moreover, the catalytic sorbent basically retains its catalytic activity and CO 2 uptake capacity after 30 cycles with merely slight deactivation. Results demonstrate that the doped Zr, presents as tetragonal ZrO 2 , enhances metal-support interactions with the formation of a Cu-O-Zr interfacial structure, promoting Cu nanocluster dispersion and altering the Cu + /Cu 0 distributions. Zr doping also enables the modulation of the medium-strong basic sites. Moreover, the AFM and TEM confirmed the formation of high-roughness MgO surface on the substrate, thereby facilitating CO 2 diffusion and adsorption. DFT calculation results further confirm the advantages of Zr-doped Cu-MgO catalytic sorbents due to its stronger capability on CH 3 OH activation and CO 2 adsorption.

研究领域: 催化化学 · 材料科学 · 能源化学
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JOURNAL OF THE ENERGY INSTITUTE · 2020 · IF 4.748

Effect of kaolinites modified with Zr and transition metals on the pyrolysis behaviors of low-rank coal and its model compound

Mei Zhong,Da Zou,Yuebing Xu,Lijun Jin,Yue Pan

Acid treated kaolinites (KA) were successively loaded with Zr and Fe, Ni or Co component to control the product distribution and upgrade the tar quality in coal pyrolysis . The structure of the resultant catalysts was characterized and their catalytic performance in the pyrolysis of demineralized low-rank coal and benzyl phenyl ether (BPE), a model compound containing C al -O bridge bond, were investigated. Results show that the introducing of Zr into the KA can enlarge the hysteresis loop due to the stacking of ZrO 2 particles. The acidities, especially the strong ones, increase as the Zr content is below 8 wt% (KA-8Z). When adding Fe, Ni or Co metals into the KA-8Z, the number of Brønsted acid sites obviously decreases, but Lewis acid sites increase. The maximum BPE conversion of 94.0% occurs for the KA-8Z, further metal-loaded sample promotes the cleavage of C al -O bond in BPE and the formation of active H radicals from CH 3 OH, leading to the increase of BPE conversion. Besides, remarkable enhancement of target monomeric aromatics is observed for the Fe, Ni and Co-loaded samples. Compared with the pyrolysis without catalyst, the tar yield as well as pitch content decrease over the KA-8Z and its metal-modified catalysts. Wherein, Ni-KA-8Z has the highest activity for tar upgrading, leading to the largest increase in the contents of light oil and phenol oil. In-situ pyrolysis by time-of-flight mass spectrometry reveals the enhanced dissociation of weak covalent bonds linked in the coal skeleton over the KA-8Z and Fe, Ni and Co-modified catalysts, resulting in a decrease in the peak temperature for product release. A marked increase in phenols and diphenols confirms a promoted dissociation of ether bond in coal.

研究领域: 化学工程 · 能源科学
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Journal of Energy Chemistry · 2016 ·Vol. 26 ·期 3 ·481-487 · IF 2.322

Amorphous Zr(OH)4 coated LiNi0.915Co0.075Al0.01O2 cathode material with enhanced electrochemical performance for lithium ion batteries

Zhen Zhang,Pengfei Zhou,Huanju Meng,Chengcheng Chen,Fangyi Cheng,Zhanliang Tao,Jun Chen

LiNi 0.915 Co 0.075 Al 0.01 O 2 (NCA) with Zr(OH) 4 coating is demonstrated as high performance cathode material for lithium ion batteries (LIBs). The coated materials are synthesized via a simple dry coating method of NCA with Zr(OH) 4 powders, and then characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Experimental results show that amorphous Zr(OH) 4 powders have been successfully coated on the surface of spherical NCA particles, exhibiting improved electrochemical performance . 0.50   wt% Zr(OH) 4 coated NCA delivers a capacity of 197.6   mAh/g at the first cycle and 154.3   mAh/g after 100 cycles with a capacity retention of 78.1% at 1 C rate. In comparison, the pure NCA shows a capacity of 194.6   mAh/g at the first cycle and 142.5   mAh/g after 100 cycles with a capacity retention of 73.2% at 1 C rate. Electrochemical impedance spectroscopy (EIS) results show that the coated material exhibits a lower resistance, indicating that the coating layer can efficiently suppress transition metals dissolution and decrease the side reactions at the surface between the electrode and electrolyte. Therefore, surface coating with amorphous Zr(OH) 4 is a simple and useful method to enhance the electrochemical performance of NCA-based materials for the cathode of LIBs.

研究领域: 电化学 · 材料科学 · 能源存储 · 电池技术 · 无机非金属材料 · 固态化学
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ENERGY & FUELS · 2021 · IF 3.605

Enhanced Thermochemical Energy Storage Stability of CaO-Based Composite Pellets Incorporated with a Zr-Based Stabilizer

Yue Zhou,Zijian Zhou,Lei Liu,Xiangyao She,Ruichang Xu,Jian Sun,Minghou Xu

Calcium looping is a potential thermochemical energy storage technology applied in a high-temperature working window. However, CaCO3/CaO materials are prone to encounter severe sintering, exhibiting poor thermal energy storage/release stability. To improve the thermochemical energy storage stability, different amounts (5, 15, and 30 wt %) of a Zr-based stabilizer were incorporated into CaCO3/CaO materials. Moreover, the graphite-casting method was adopted to prepare the Zr-stabilized, CaO-based composite pellets aiming to improve the practicability. The incorporation of the Zr-based stabilizer can effectively resist the sintering of CaO-based composite powders during a high-temperature precalcination process. It is mainly attributed to the large amounts of generated, nanosized CaZrO3 grains possessing desirable antisintering ability evenly distributed within the composites. Particularly, the Zr-stabilized, CaO-based composite pellets containing 30 wt % of CaZrO3 possess a relatively high compression strength of 2.28 ± 0.87 MPa and a desirable thermal storage density of 1.15 GJ/t after 20 cycles. Additionally, the graphite-casted, Zr-stabilized, CaO-based composite pellets have potential to be applied in a large-scale thermochemical energy storage system because the graphite-casting method is easy to be scaled-up.

CAS / MDL: 5949-29-1
研究领域: 材料科学 · 储能技术 · 热能工程
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APPLIED ORGANOMETALLIC CHEMISTRY · 2025 ·Vol. 39 ·期 3 ·e70008 · IF 0

Photocatalytic Degradation of Typical Bisphenol Compounds Using Zr-NiFe2O4@ZIF-67/ZIF-8 in Collaboration With Peroxydisulfate/Peroxymonosulfate

Yawen Wu,Xueying Hou,Ao Li,Ruijian Li,Qingqing Yang,Shaohua Jiang,Jing yu Hu,Qingliang You,Rui Guo

As the amount of tetrachlorobisphenol A (TCBPA) that causes potential adverse effects on human health in the environment is continually increasing. It is therefore important to develop new materials for the adsorption or degradation of these compounds using various techniques. In this study, two novel magnetic recyclable composite catalysts Zr–NiFe 2 O 4 @ZIF-67 and Zr–NiFe 2 O 4 @ZIF-8 were synthesized. These catalysts degraded tetrachlorobisphenol A (TCBPA) in water by activating peroxydisulfate (PDS)/peroxymonosulfate (PMS), respectively. The results show that the Zr–NiFe 2 O 4 @ZIF-67-5%/LED/(NH 4 ) 2 S 2 O 8 system can degrade 95% of TCBPA (20 mg/L) within 30 min, whereas the Zr–NiFe 2 O 4 @ZIF-8-10%/LED/KHSO 5 system degrades 90% of TCBPA within 30 min. In instances of metal leaching at low concentrations, nickel and iron ions declined to 0.008 mg·L −1 , TCBPA exhibits highly efficient and sustainable catalytic properties, maintaining over 80% efficacy across six cycles. The online infrared test experiment results showed the major functional groups disappearing within approximately 130 s. The results of electron paramagnetic resonance and free-radical-quenching experiments showed that SO 4 ˙ − , ˙OH, 1 O 2 , and O 2 ˙ − were involved in the degradation of TCBPA. The possible degradation paths are isomerization polymerization, dechlorination, hydroxylation, ring-opening by oxidation, and further transformation into small molecules of acids, aldehydes, alcohols and other compounds. Thus, in this study, a reliable technique for the degradation of halogenated bisphenol compounds is developed. Overall, the photocatalytic degradation of organic pollutants in water utilizing polymetallic composites as catalysts represents an innovative approach to water treatment, demonstrating enhanced catalytic activity and recyclability, with promising prospects for significant advancements in both theoretical research and practical applications.

研究领域: 环境科学 · 材料科学 · 化学工程
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Rapid one-pot synthesis of multifunctional UiO-66(Zr/Ce)-NH2 for detection and photocatalytic degradation of tetracycline

Chaoting Shi,Ninghan Tang,Shan Pu,Hui Xin,Lan Wu,Xiandeng Hou

Metal-Organic Frameworks (MOFs) have been widely used for the antibiotic pollution control. However, it remains a challenge to simple design and synthesis of multifunctional MOFs for sensing and degradation antibiotics. Herein, a multifunctional UiO-66(Zr/Ce)-NH 2 ratiometric fluorescence sensing and photocatalytic degradation platform was rapidly and simply constructed at room temperature by a one-pot method using a dielectric barrier discharge device. The mixed-metal centers and mixed-ligands of this platform enabled effective ratiometric fluorescence sensing of tetracycline (TC), along with a visual fluorescence shift from blue to yellow-green color. The platform demonstrated a detection of TC ranged from 200 nM to 15 μM, with a detection limit of 43 nM. Moreover, the UiO-66(Zr/Ce)-NH 2 exhibited strong light absorption and efficient photogenerated carrier separation, thus offering excellent degradation performance of TC compared with that of MOFs with single metal center, mixed ligands or mixed metal centers. The mechanism of fluorescence detection and potential charge transfer pathways by the UiO-66(Zr/Ce)-NH 2 were analyzed. This work provided a new approach for the simple design and synthesis of multifunctional MOFs platforms.

研究领域: 环境科学 · 材料科学 · 化学工程
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Journal of Materials Chemistry B · 2015 ·Vol. 3 ·期 20 ·4242-4248 · IF 4.726

Zr-based metal–organic frameworks for specific and size-selective enrichment of phosphopeptides with simultaneous exclusion of proteins

Xiangyang Zhu,Jinlou Gu,Jian Yang,Zhe Wang,Yongsheng Li,Liming Zhao,Wenru Zhao,Jianlin Shi

The accurate characterization of low abundance phosphopeptides based on mass spectrometry (MS) techniques remains a challenge due to signal suppression by the large excess of interfering proteins and non-phosphopeptides. This demands better methods to effectively enrich phosphopeptides prior to MS analysis. In the current work, facilely synthesized Zr-based metal–organic frameworks (MOFs) of UiO-66 and UiO-67 have been successfully exploited as novel affinity materials for the enrichment and analysis of phosphopeptides. Thanks to their abundantly existent and naturally exposed Zr–O clusters, intrinsically large surface areas and highly ordered open cavities, UiO-66 and UiO-67 exhibited sensitive and specific enrichment of phosphopeptides with an interesting molecular sieving effect. An optimized protocol for loading, washing and elution was developed. Under these most optimized conditions, specific accumulation was demonstrated by the selective enrichment of phosphopeptides in the presence of abundant non-phosphorylated species. Meanwhile, high-abundance interfering proteins could be effectively excluded during the enrichment process. Additionally, the MOFs have also been successfully used to enrich phosphopeptides from human serum. These merits combined with their high chemical and thermal stabilities, make UiO-66 and UiO-67 highly promising for applications in phosphopeptidome research.

研究领域: 生物化学 · 分析化学 · 蛋白质组学
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