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PROCESS BIOCHEMISTRY · 2024 · IF 3.7

Immobilized lipase post-encapsulated in Cu-based MOFs with promoted stability in biodiesel synthesis

Hongbo Suo,Xinzheng Liu,Shu Chen,Qi Li,Xiangnan Liu,Lili Xu

Biodiesel is more environmentally friendly compared to traditional petroleum diesel. The method of producing biodiesel catalyzed by lipases, as a green chemistry technology, can further reduce its negative impact on the environment. In this work, lipase immobilized on magnetic cellulose was embedded in Cu(PABA), and then the biocomposite (MCL@Cu(PABA)) was used for biodiesel production. The good biocompatibility and flexible skeleton structure of cellulose can buffer the compression effect on enzyme molecules during the formation of Metal-Organic Frameworks (MOFs), and the MOFs protective layer can reduce the damage caused by denaturants to enzyme molecules. The biocatalyst showed enhanced activity and stability with a lower deactivation constant ( K d ). Under the optimized reaction conditions, the biodiesel yield can reach 78.4 %. After reused for 7 times, the biocatalyst can still achieve a biodiesel yield of 58.8 %. Moreover, after stored for 30 days, the biodiesel yield can still reach 70.3 %. For all experimental yields, the standard deviation (SD) ranged from 2.4 % to 4.5 %. Secondary structure analysis showed that the rigid structure and active conformation of lipase was enhanced after Cu(PABA) encapsulation.

研究领域: 生物化学 · 环境科学
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

High Thermoelectric Performance in Cu-Doped Bi2Te2.7Se0.33 Due to Cl Doping and Multiscale AgBiSe2

Abubakar Yakubu Haruna,Yubo Luo,Zheng Ma,Wang Li,Haiqiang Liu,Xin Li,Qinghui Jiang,Junyou Yang

The thermoelectric performance of n-type Bi2Te3 needs further enhancement to match that of its p-type Bi2Te3 counterpart and should be considered for competitive applications. Combining Cu/Cl and multiscale additives (AgBiSe2) presents a suitable route for such enhancement. This is evidence of the enhanced thermoelectric performance of Bi1.995Cu0.005Te2.69Se0.33Cl0.03. Moreover, by incorporating 0.65 wt % AgBiSe2 (ABS) into Bi1.995Cu0.005Te2.69Se0.33Cl0.03, we further reduce its lattice thermal conductivity to ∼0.28 W m–1 K–1 at 353 K owing to the extra phonon scattering of multiscale ABS. Additionally, the Seebeck coefficient enhances (−183.89 μV K–1 at 353 K) owing to the matrix’s reduced carrier concentration caused by ABS. As a result, we achieve a high ZT of ∼1.25 (at 353 K) and a high ZTave of ∼1.12 at 300–433 K for Bi1.995Cu0.005Te2.69Se0.33Cl0.03 + 0.65 wt % ABS. This work provides a promising strategy for enhancing the thermoelectric performance of n-type Bi2Te3 through Cu/Cl doping and ABS incorporation.

研究领域: 材料科学 · 能源材料 · 热电材料优化
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2015 ·Vol. 17 ·期 37 ·24361-24369 · IF 4.493

Growth of Cu particles on a Cu2O truncated octahedron: tuning of the Cu content for efficient glucose sensing

Gang Wang,Hong Sun,Lu Ding,Gang Zhou,Zhong-Sheng Wang

A simple and versatile hydrothermal method is developed to synthesize Cu–Cu2O, in which Cu particles grow on the surface of a Cu2O truncated octahedron. Through the reduction of Cu2+ by glucose in an alkaline solution, the Cu2O truncated octahedron is quickly formed via a kinetic control process, and then Cu particles selectively nucleate on the high-energy (110) facets of Cu2O, generating a heterostructure. The amount of Cu in the sample is successfully tuned by varying the reaction temperature. Compared to Cu2O, the hybrid Cu–Cu2O architecture shows superior electrocatalytic performance for glucose oxidation due to the synergistic effect between more electrocatalytic active but less conductive Cu2O and more conductive but less electrocatalytic active Cu. By tuning the content of Cu in the heterostructure, the highest electrocatalytic activity is achieved at the Cu/Cu2O molar ratio of 0.83.

研究领域: 材料科学 · 电化学 · 纳米技术
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Catalysis Science & Technology · 2022 ·Vol. 12 ·期 19 ·5879-5890 · IF 6.177

Ring-opening of furfuryl alcohol to pentanediol with extremely high selectivity over Cu/MFI catalysts with balanced Cu0–Cu+ and Brønsted acid sites

Dengfeng Dai,Chao Feng,Minmin Wang,Qingzhou Du,Dandan Liu,Yuan Pan,Yunqi Liu

Biomass-based chemicals as a renewable alternative to petroleum-based chemicals are of great significance. The conversion of biomass-based furfuryl alcohol to pentanediol, including 1,5-pentanediol and 1,2-pentanediol, is explored over a series of bifunctional Cu/MFI catalysts in a continuous-flow reactor. These catalysts are synthesized by supporting copper nanoparticles on MFI zeolites with varying molar ratios of SiO2/Al2O3. Among them, the Z60-10Cu catalyst containing balanced Cu0–Cu+ and Brønsted acid sites exhibits excellent performance, and a high furfuryl alcohol conversion of 99.5% and selectivity of 85.2% for 1,5-pentanediol (69.2%) and 1,2-pentanediol (16.0%) could be achieved (hydrogen pressure: 2.5 MPa) at 160 °C. The experimental results and the results obtained using the DFT technique revealed that the high catalytic activity realized during the processes of ring-opening and hydrogenation could be attributed to the synergistic effect between the Cu species and Brønsted acid sites. The Brønsted acid sites on the Si(OH)Al groups significantly affect the ring-opening process of furfuryl alcohol. The methoxy group on furfuryl alcohol adsorbs on the Cu+ sites, and the hydrogenation saturation of the ring-opening intermediate is realized under the influence of the activated hydrogen units on the Cu0 sites. The results reported herein could help promote the continuous production of high value-added pentanediol from biomass-based raw materials in the presence of non-noble metal catalysts. An economical and feasible path for the transformation of biomass resources into high value-added fine chemicals could also be developed.

CAS / MDL: 98-00-0 97-99-4
研究领域: 生物化学 · 催化化学 · 材料科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Zinc and phosphorus poisoning tolerance of Cu-SSZ-13 and Ce-Cu-SSZ-13 in the catalytic reduction of nitrogen oxides

Kunli Song,Shuqi Zhao,Zhenguo Li,Kaixiang Li,Yurong Xu,Yijun Zhang,Yonghong Cheng,Jian-Wen Shi

SSZ-13 has been commercialized as a catalyst in diesel engines for the selectivity catalytic reduction of nitrogen oxides (NO x ) with ammonia (NH 3 -SCR), but the catalyst is facing the problem of poisoning. Herein, two well-designed catalysts, Cu-SSZ-13 and cerium (Ce) doped Cu-SSZ-13 are synthesized, and their tolerance to zinc (Zn) and phosphorus (P) poisoning alone and together are explored in detail. The research found that Zn and P poisoning alone leads to the destruction of Cu-SSZ-13 structure, resulting in the decline of denitration (de-NO x ) performance following the mechanism dominated by Eley-Rideal (E-R). Surprisingly, it is found that zinc phosphate particles are formed at inactive sites on the surface of Cu-SSZ-13 in the presence of Zn and P together, which protects the active sites, enhances the adsorption of nitric oxide. As a result, the excellent de-NO x performance of Cu-SSZ-13 is well maintained following the dual mechanism of E-R and Langmuir-Hinshelwood (L-H). In addition, the introduction of Ce stabilizes the active sites, so as to improve the de-NO x performance and the poisoning tolerance of Cu-SSZ-13. This work deeply analyzes the reasons of Zn and P poisoning and the positive effect of Ce on Cu-SSZ-13, which provides ideas for improving the poisoning tolerance of Cu-SSZ-13 and promotes the further application.

研究领域: 环境科学 · 催化化学
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CATALYSIS TODAY · 2018 · IF 4.667

The Cu migration of Cu-SAPO-34 catalyst for ammonia selective catalytic reduction of NOx during high temperature hydrothermal aging treatment

Xianghui Li,Yingnan Zhao,Huawang Zhao,Mengke Liu,Yuhan Ma,Xin Yong,Hong Chen,Yongdan Li

Two kinds of Cu-SAPO-34 catalysts, prepared with a one-pot technique using Cu- tetraethylenepentamine as co-template and an ion-exchange method, were hydrothermally treated at 750 °C for at least 16 h. The migration of Cu species during hydrothermal treatment and the corresponding effect on the selective catalytic reduction (SCR) of NO x were examined and characterized. A certain amount of CuO exists outside and inner the crystallites in the as prepared ion-exchanged sample, whereas copper is mainly atomically dispersed in the one-pot sample existing as isolated Cu 2+ . After hydrothermal treatment for 16 h, the amount of the inner nanosized CuO in the ion-exchanged sample reduced and the copper disperses to form more isolated Cu 2+ . However, surface CuO particles increase at the sacrifice of isolated Cu 2+ with extending the hydrothermal treatment to 24 h. Aggregation of Cu 2+ species also happens during the aging treatment over the one-pot prepared sample where the initial Cu is atomically dispersed as isolated Cu 2+ . The increase of the amount of the isolated Cu 2+ enhances the low-temperature (< 350 °C) performance. However, the increase of the amount of surface CuO particles in the aged samples promotes the nonselective NH 3 oxidation reaction in the high temperature range and results in the lowering of the SCR activity by limiting NH 3 supply.

CAS / MDL: 109-89-7
研究领域: 环境科学 · 催化化学
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Journal of Materials Chemistry A · 2024 · IF 10.7

Dual single-atom sites coupled with graphene-encapsulated core–shell Fe–Cu nanoalloy for boosting the oxygen reduction reaction

Katam Srinivas,Zhuo Chen,Anran Chen,He Huang,Chengtao Yang,Fei Wang,Ming-qiang Zhu,Yuanfu Chen

Replacing platinum-based electrocatalysts with iron single-atom catalysts (Fe–N4–C) for the oxygen reduction reaction (ORR) remains challenging due to the symmetric electronic structure of atomically dispersed Fe–N4 sites and sluggish kinetics. To address this issue, we introduce Cu–Nx sites and graphene-encapsulated core–shell Fe–Cu nanoalloy (FeCu@G) particles into the Fe–Nx site surroundings through the self-assembly and pyrolysis of a metal–organic framework (MOF). This strategy leverages synergistic interactions with the associated species to modify the uniform electronic structure of Fe single-atom sites, thereby enhancing oxygen-adsorption/desorption kinetics. Density functional theory (DFT) calculations reveal that the incorporation of Cu–Nx sites and FeCu@G nanoalloy particles significantly alters the electronic structure of Fe–Nx sites, leading to improved ORR activity. Consequently, the optimized FeCu-DSAs@CNT, comprising dual single-atom sites (DSAs: Fe–Nx and Cu–Nx) and FeCu@G nanoalloy within MOF-derived nitrogen-doped carbon nanotubes (CNTs), exhibits a significantly improved half-wave potential (E1/2 = 0.91 V) and feasible ORR kinetics (Tafel slope = 48.15 mV dec−1), surpassing the Pt/C benchmark (E1/2 = 0.847 V and Tafel slope = 56.76 mV dec−1). Notably, FeCu-DSAs@CNT shows a 58 mV more positive E1/2 compared to monometallic Fe–SAs@CNT, attributed to synergistic interactions with Cu species. Moreover, it demonstrates excellent power density, specific capacity, and cycling stability in a lab-made zinc–air battery, outpacing the Pt/C-battery. This study addresses gaps in understanding Fe–Nx site interactions with associated species, providing valuable insights for the advancement of Fe–Nx–C electrocatalysts.

研究领域: 材料科学 · 电化学
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IONICS · 2024 ·Vol. 30 ·期 3 ·1615-1625 · IF 2.4

Cu-MOF-derived Cu2V2O7@C nanofilm for electrochromic properties

Dong Jinxiu,Cui Shichuang,Wang Fei,Wei Wei,Yin Ziluo,Zhang Yuqing,Zhu Quanyao

Electrochromism (EC) is a color control technique for providing visual information, in which vanadium pentoxide (V 2 O 5 ) is a promising material for electrochromic applications due to its excellent ionic intercalation/deintercalation properties and cathodic/anodic color-changing properties. However, its poor cycling stability and color change response rate limit its practical application. Metal–organic frameworks (MOFs) combine the rigidity and flexibility of inorganic–organic materials and can meet the requirements of EC materials such as cycle stability, electrical conductivity, and stress-interference resistance. We report here a strategy to modify V 2 O 5 with Cu-MOF. Cu-doped V 2 O 5 and carbon skeleton (Cu 2 V 2 O 7 @C) composites were prepared for electrochromism. In this scheme, Cu doping can facilitate lithium ion migration by broadening and stabilizing the structure of V 2 O 5 , and the distribution of the carbon skeleton can broaden the contact of the active material with the electrolyte and improve the electron conduction. Combining these merits, it exhibits excellent long-term cycle stability (the capacity retention rate reaches 91.78% after 2000 cycles), the light transmission modulation is greatly improved compared with V 2 O 5 (Δ T  = 69%, doubled), and the response time is reduced by 30.43%. This study provides a new perspective for improving the light modulation ability and long-term use stability of vanadium oxide EC materials and promotes the development of MOF materials in the field of electrochromism.

研究领域: 材料科学 · 电化学
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MOLECULES · 2024 ·Vol. 29 ·期 8 ·1721 · IF 4.2

Study of CHF3/CH2F2 Adsorption Separation in TIFSIX-2-Cu-i

Shoudong Wang,Lei Zhou,Hongyun Qin,Zixu Dong,Haoyuan Li,Bo Liu,Zhilu Wang,Lina Zhang,Qiang Fu,Xia Chen

Hydrofluorocarbons (HFCs) have important applications in different industries; however, they are environmentally unfriendly due to their high global warming potential (GWP). Hence, reclamation of used hydrofluorocarbons via energy-efficient adsorption-based separation will greatly contribute to reducing their impact on the environment. In particular, the separation of azeotropic refrigerants remains challenging, such as typical mixtures of CH2F2(HFC-23) and CHF3(HFC-32), due to a lack of adsorptive mechanisms. Metal–organic frameworks (MOFs) can provide a promising solution for the separation of CHF3–CH2F2mixtures. In this study, the adsorption mechanism of CHF3–CH2F2mixtures in TIFSIX-2-Cu-i was revealed at the microscopic level by combining static pure-component adsorption experiments, molecular simulations, and density-functional theory (DFT) calculations. The adsorption separation selectivity of CH2F2/CHF3in TIFSIX-2-Cu-i is 3.17 at 3 bar under 308 K. The existence of similar TiF62−binding sites for CH2F2or CHF3was revealed in TIFSIX-2-Cu-i. Interactions between the fluorine atom of the framework and the hydrogen atom of the guest molecule were found to be responsible for determining the high adsorption separation selectivity of CH2F2/CHF3. This exploration is important for the design of highly selective adsorbents for the separation of azeotropic refrigerants.

CAS / MDL: 16962-40-6 67-56-1
研究领域: 材料科学 · 环境科学 · 化学工程
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ADVANCED POWDER TECHNOLOGY · 2022 · IF 4.969

Preparation and properties of Al2O3 dispersed fine-grained W-Cu alloy

He Zhang,Jun-Ru Liu,Zhi-Bo Li,Xiao-Chun Deng,Guo-Hua Zhang,Kuo-Chih Chou

In this study, high-performance fine-grained W-Cu sintered blocks with the addition of dispersed Al 2 O 3 particles were successfully produced by low temperature liquid-phase sintering, using the raw material of ultrafine W-Cu alloy powder. The ultrafine W-Cu alloy powder was obtained by a two-step reduction process composed of stages of carbothermal reaction and hydrogen deep deoxidation. The fine Al 2 O 3 grains with uniform distribution in W-Cu alloy were introduced by spray method, leading to the decrease of W grain size and W-W connectivity. The relative densities of all sintered blocks were>97%, and a higher degree of densification ensures that the alloy has excellent comprehensive properties. With the increase of Al 2 O 3 content, W grain size and W-W connectivity of sintered W-Cu samples decrease from 664 nm to 472 nm and 0.2 to 0.14, respectively. The W-Cu alloy with the ultimate tensile strength of 415 MPa and the highest elongation of 7.22% was obtained when the addition amount of Al 2 O 3 was 0.5 wt%. At the same time, it also possessed the maximum bending strength of 1028 MPa and microhardness of 312 HV, respectively. In addition, due to the good network structure of Cu and uniform three-phase distribution, the sintered samples had excellent conductivity and compressive strength.

CAS / MDL: 7784-27-2
研究领域: 材料科学 · 冶金工程
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Configuration modulation of vermiculite by exfoliation coupled Cu(II) anchoring for boosting removal of tetracycline via synergy of adsorption and photocatalysis

Ping Zhang,Mingxue Xiang,Wei Jiang,Huiling Liu,Yu Chen,Ying Fang,Longyong Wu,Hongjun Guo,Yufei Wang

Integrated adsorption and photocatalysis is a worth frontier strategy for recalcitrant organics elimination, yet the current challenge is developing materials featured with dual functions of adsorption/photocatalytic ability. In this scenario, a novel attractive exfoliated vermiculite coupling with Cu(II) composite (eVT@Cu) was tactfully engineered. Specifically, exfoliated structure containing vast negative charge was conductive for Cu(II) loading. The anchored Cu(II) played triple roles in this system, that is, regulating electron configuration of photocatalyst with narrow bandgap, as well as providing complexation sites for tetracycline (TC) enrichment. With the help of inherent Fe(III), Cu(II) was readily to form heterogeneous high-valence Cu(III) driven by photonic energy. Benefited by these effects, eVT@Cu exhibited extremely augment on TC removal compared to pristine VT and eVT, with ca. 80% removal efficiency through the synergy of adsorption and photocatalysis. Overall, this study not only provides an excellent environmental candidate for TC removal but also opens a brand-new perspective for the generation of heterogeneous high-valence Cu(III) over eVT@Cu under visible light.

研究领域: 环境科学 · 材料科学 · 化学工程
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

In-situ decoration of unsaturated Cu sites on Cu2O photocathode for boosting nitrogen reduction reaction

Ying Liu,Hongye Bai,Qianxiao Zhang,Yajie Bai,Xuliang Pang,Fagen Wang,Yingchen Yang,Jinrui Ding,Weiqiang Fan,Weidong Shi

Photoelectrochemical N 2 reduction reaction (PEC NRR) into chemical energy source is a promising technique for solving environmental challenges and the energy crisis, which depends on the exploration of p-type photocathodes. Cu 2 O is a p-type semiconductor, which can be applied as a photocathode for PEC NRR. However, the adsorption and activation ability of N 2 over the pristine Cu 2 O is still not ideal, causing the overall efficiency far below the theoretical value. In this work, we first proposed a feasible strategy to in-situ modify the surface of Cu 2 O with Cu-MOF, and the Cu-MOF/Cu 2 O heterostructure exhibited the significantly boosted NH 3 production rate (7.16 mmol/m 2 /h). The ultra-thin Cu-MOF film takes a nature of porous structure and unsaturated Cu sites, contributing to a favorable interface environment for the adsorption and activation of N 2 . The N 2 temperature programmed desorption and contrast photocurrent curves revealed the desirable selectivity for PEC NRR, and the isotope NMR further confirmed the accuracy of NH 3 evolution process. Therefore, the organic–inorganic hybrid systems built from Cu-MOF and Cu 2 O would offer a new insight for establishing the efficient PEC NRR system.

CAS / MDL: 554-95-0
研究领域: 材料科学 · 环境科学 · 化学工程
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