Environmental Science-Nano
·
2024
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IF 5.8
Jingwei Hong,Wanli Li,Jin Shang,Hiromi Yamashita,Yun Hu
Utilizing electrocatalysis to convert CO2 into high-value industrial raw materials can not only effectively reduce CO2 emissions but also achieve a closed carbon cycle. This method holds great potential for addressing global warming and alleviating the fossil fuel crisis. Here, we report a novel electrocatalyst for CO2 reduction composed of a composite material derived from Cu-MOF74 and Cu2O, synthesized under the regulation of an appropriate amount of KOH. The research results indicate that the unique Cu0/Cu+ interface in Cu-MOF74/Cu2O-350 enhances the adsorption of reaction intermediates, providing more active sites for CO2 reduction. Additionally, the moderate carbonization during the thermal treatment process increases conductivity and enriches the electrochemical active surface area, accelerating the charge transfer rate. Consequently, this composite exhibits excellent CO2 reduction performance. At -1.3 V vs. RHE, the Faraday efficiency (FE) for C2H4 production reached up to 32.48%, which was significantly higher than that of pure Cu2O-350 (9.25%) and Cu-MOF74-350 (15.52%). Even after 6 hours of reaction, the FE for C2H4 remained above 24.52%, reflecting its good stability. Furthermore, we utilized in-situ infrared spectroscopy to study the key intermediates of the relevant reduction products, inferring the possible reaction pathways for the formation of HCOOH and C2H4. This study provides a simple synthesis method for the preparation of high-selectivity MOF-derived composite catalysts for the electrocatalytic reduction of CO2 to value-added chemicals.
研究领域:
电化学
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材料科学
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环境科学
·
催化
✓ 已验证
产品关联
DOI
高影响因子
CHEMOSPHERE
·
2022
·
IF 8.943
Cheng-Feng Liang,Song-Hai Wu,Yu-Le Wang,Zhi Xu,Yong Liu,Hai-Tao Ren,Shao-Yi Jia,Xu Han
Thiosulfate (S 2 O 3 2− ) is an important ligand to complex metal cations, however, the reactivity of metal-thiosulfate complexes has barely been mentioned. In this study, the reactivity of the Cu(II)–S 2 O 3 2− system in the reduction of Cr(VI) was investigated. Kinetic results show that the reduction rates of Cr(VI) decrease with increasing pH values from 3.0 to 5.0, and 94.3% and 97.5% of 10 mg L −1 Cr(VI) was rapidly reduced within 1 min at pH 3.0 and within 30 min at pH 5.0, respectively at the molar ratio of Cu(II):S 2 O 3 2− of 0.05. We rule out the contributions of S species of tetrathionate (S 4 O 6 2− ) and sulfite (SO 3 2− ) to Cr(VI) reduction and point out that the produced Cu(I) in the Cu(II)–S 2 O 3 2− system is the key reductant that mediates the reduction of Cr(VI). We suggest that complexation between Cu(II) and S 2 O 3 2− with the formation of Cu II (S 2 O 3 ) 2 2− is the pre-requisite for the formation of Cu I (S 2 O 3 ) n 1−2n , which plays an important role in Cr(VI) reduction, accompanied by the re-oxidation of Cu(I) to Cu(II) by Cr(VI), achieving the rapid redox cycling of Cu(II)–Cu(I)–Cu(II). Such a redox cycle also mediates the denitrification process of NO 2 − to NH 3 /NH 4 + under weakly acidic conditions. This study enriches our understanding on the reducing reactivity of the Cu(II)–S 2 O 3 2− system and the importance of the Cu(II)–Cu(I)–Cu(II) redox cycle towards environmental oxidizing contaminants.
研究领域:
环境化学
·
配位化学
✓ 已验证
DOI
PubMed
高影响因子
ENERGY & FUELS
·
2024
·
IF 5.2
Yongjin Wang,Zhipeng Zhou,Xiaoxia Zhang,Junjie Liao,Jiancheng Wang,Weiren Bao,Liping Chang
The preparation of a Cu-based sorbent supported by cost-effective AlOOH is proposed. A Cu-based sorbent for thiophene removal from coke oven gas was synthesized via coprecipitation, and the effect of AlOOH addition on the dispersion of activated Cu species and desulfurization properties was investigated. At an AlOOH content of 25%, smaller and more highly dispersed Cu grains, along with ZnO crystalline phases, were present on the surface of the Cu-based sorbent. The enhanced Cu-ZnO interaction contributed to the superior desulfurization performance (Qb-thiophene = 30.43 mg/g). The incorporation of an appropriate amount of AlOOH into the binary system during synthesis produces a highly active sorbent with superior Cu dispersion and smaller Cu grains, thereby fulfilling the requirements of industrial applications at a lower production cost.
研究领域:
化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Zhen Huang,Ziyang Chu,Haibo Liu,Tianhu Chen,Xuehua Zou,Fuwei Sun,Dong Chen
Effective removal of heavy metal complexes from contaminated water remains a challenging task. In this work, a limestone/PMS system was constructed for the efficient degradation of Cu-EDTA. Under the conditions of 3.0 g/L limestone and 1.0 mM PMS, the degradation efficiency of 10.0 mg/L Cu-EDTA reached 99.0 % in 60 min, and the removal efficiency of Cu ions approached 50.0 %. The main active specie revealed by quenching and EPR experiments was the singlet oxygen ( 1 O 2 ). Interestingly, Trace amounts of Cu(II) in limestone react with PMS enhancing the degradation of Cu-EDTA. The results of the HPLC-MS analysis showed that the reactive species attacked the Cu–O and Cu–N bonds, as well as triggered a decarboxylation process, resulting in the decomposition of Cu-EDTA into six intermediates. Meanwhile, SEM and XPS analyses revealed that Cu ions released during the degradation of Cu-EDTA are deposited on the limestone surface as Cu(OH) 2 and Cu 2 (OH) 2 CO 3 . In addition, the initial pH and co-existing ions have a weak effect on the system. Finally, a one-month continuous flow experiment showed that the degradation efficiency of Cu-EDTA was about 95.0 % and the removal efficiency of Cu ions was 40.0 %. In conclusion, this study provides a new approach for the destruction of metal complexes and the removal of heavy metals.
研究领域:
环境科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Lei Xiao,Chaowei Yuan,Peng Chen,Yongyi Liu,Jianping Sheng,Shihan Zhang,Fan Dong,Yanjuan Sun
Due to the intrinsic chemically inert CO2 with the dissociation energy of C═O bond as high as 750 kJ mol–1, low efficiency and selectivity have become the most significant restraints for the practical application of photocatalytic CO2 reduction. Renewing the electronic structure of adsorbed CO2 on the catalyst surface through a rational catalyst design is crucial to achieving performance improvement. Herein, we prepared ZnIn2S4 and Cu-substituted ZnIn2S4 containing both Lewis acid and Lewis base sites as a model system for investigating the activation of CO2 by M–S chemical bonds (M represents a metal site). The Cu–S chemical bond can effectively activate CO2 as a vital electron channel and lower the Gibbs free energy for generating the essential intermediate *COOH. Besides, the Cu0.7-ZnIn2S4 sample displays 74.8% selectivity for reducing CO2 to CO with a rate of 47.2 μmol g–1 h–1, roughly 7.14 times that of ZnIn2S4.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2024
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IF 12.2
Ziyang Chu,Zhengyan Han,Haibo Liu,Tianhu Chen,Xuehua Zou,Hanlin Wang,Fuwei Sun,Hao Wang,Dong Chen
The simultaneous removal of heavy metal complexes (HMCs) and heavy metal ions presents a significant challenge in treating wastewater. To address this, we propose a Calcite/Peroxymonosulfate (Calcite/PMS) system aimed at simultaneously decomplexing Cu-EDTA and removing Cu ions . Calcite/PMS system could achieve 99.5 % Cu-EDTA decomplexation and 61.9 % Cu ions removal within 60 min under initial conditions of Cu-EDTA (10 mg/L), Calcite (3 g/L), and PMS (2 mM). Singlet oxygen ( 1 O 2 ) emerged as the predominant reactive species responsible for Cu-EDTA decomplexation, which selectively targeted the N-C bonds in the Cu-EDTA structure to produce intermediates with lower biotoxicity than EDTA. Interestingly, solid phase Cu(III) (≡Cu(III)) promoted the generation of superoxide radicals (O 2 •− ) with a contribution of up to 72.8 %. Subsequently, nascent ≡Cu(III) and O 2 •− accelerated the degradation of intermediates. Besides, coexisting organic substances inhibited Cu-EDTA decomplexation, whereas inorganic ions had a weak impact. After five cycles of use, the Calcite/PMS system retained 99.3 % efficiency in decomplexing Cu-EDTA. This investigation provides valuable insights into using calcite to remove HMCs and enhances our comprehension of the decomplexation intermediates accelerating HMCs degradation.
研究领域:
环境科学
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化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Mei-Yao Wu,Shan-Qing Li,Wei-Wei Wang,Chun-Jiang Jia
The structures of active components in practical solid catalysts are seldom homogeneous, which makes it challenging to explore the synergistic effect among the complex catalyst components in heterogeneous catalysis. The active structure of Cu-based catalysts, which are widely used in water gas shift reactions and other important industrial reactions, has been debated. This work prepared Cu–MgO catalysts with the copresence of Cu particles and Cu atoms to investigate the synergistic effects of these Cu species. We found that the Cu nanoparticles served to adsorb and activate the reactant molecule of CO, while the atomic Cu species at the surface of the MgO lattice might exist as the Mg2Cu2–Ov site for water dissociation. The presence of surface-substituted Cu atoms modulated the reactivity of adjacent oxygen vacancy in the MgO surface, enhanced the ability of H2O dissociation to form reactive –OH species, and allowed the oxygen vacancies to recycle, contributing to the continuation of the reaction. A volcano-type relation of catalytic performance versus Cu0/Cu2+ ratio has been established, revealing the existence of synergy between Cu particles and Cu atoms. In addition, due to this synergistic effect, the optimized Cu–MgO catalyst shows a very high activity with a CO conversion rate of 1119 μmolCO gCu–1 s–1 at 300 °C. This work revealed the synergistic effect of different Cu species in the Cu–MgO catalysts, which was important for unraveling the contribution of complex components to catalytic performance.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
·
IF 16.744
Jingang Wang,Jianbo Zhang,Cheng Xing,Taosheng Jin,Jinpeng Liu,Meiting Ju,Xuejiao Tang
Phosphorus (P) poisoning of NH 3 -SCR catalysts is inevitable in application of NO x abatement of diesel exhaust. The distinct effects on Cu-SSZ-13 of P from different precursors (H 3 PO 4 and (NH 4 ) 2 HPO 4 ) were figured out and the mechanism was further investigated. P-poisoned Cu-SSZ-13 (Si/Al = 6) catalysts were prepared and characterized using N 2 adsorption, X-ray powder diffraction (XRD), scanning electron microscope with energy-dispersive X-ray spectroscopy mapping (SEM-EDX), ammonia temperature-programmed desorption (NH 3 -TPD), X-ray photoelectron spectroscopy (XPS), hydrogen temperature programmed reduction (H 2 -TPR), electron paramagnetic resonance (EPR) and 27 Al solid-state magic angle spinning nuclear magnetic resonance spectroscopies ( 27 Al NMR). Significant enhancement of high-temperature activities (400–600 °C) were observed for the catalysts with P loading of 0.3–0.9 wt%, since the appropriate incorporation enabled to bind P atoms to CuO x in remained framework. However, the high P content of 1.5 wt% resulted in a detrimental effect on framework to induce the accumulation of Cu species. Interestingly, the dominant P from H 3 PO 4 was inclined to directly attack the framework Al leading to more severe dealumination, while the P from (NH 4 ) 2 HPO 4 interacted with Cu 2+ to form copper phosphate with more Cu 2+ migrating to the surface of the catalyst which promoted the NO x conversation at each active site resulting in the low-temperature catalytic activity unchanged. So, control of the P/Cu and form of P is capable of preventing P poisoning and unlocks the potential of Cu-SSZ-13 in exhaust treatment.
研究领域:
环境科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COORDINATION CHEMISTRY
·
2021
·
IF 1.751
Yan Zhao,Xianying Duan,Guangguang Zhang,Meilin Wei
Two proton-conductive and luminescent organic-inorganic hybrid materials, {[Cu(II)(bhmbpy)(H2O)(Cl)0.5(CH3CN)]2[PW(VI)10W(V)2O39]}·4H2O(1) and {H2[Cu(I)(bhmbpy)2(Cl)Cu(I)(bhmbpy)2][PW12O40]}·7H2O (2) (where bhmbpy is bis(hydroxymethyl)-2,2′-bipyridine), were synthesized at room temperature. The two products were characterized by infrared spectroscopy, X-ray single-crystal diffraction, X-ray powder diffraction, elemental and thermogravimetric analyses. The proton conductivities and luminescence of 1 and 2 were studied by using alternating-current impedance spectroscopy and luminescence spectroscopy, respectively. X-ray diffraction analysis revealed that 1 includes a decorated polyanion chain {[Cu(II)(bhmbpy)(H2O)(Cl)0.5(CH3CN)]2[PW(VI)10W(V)2O39]}n and forms a three-dimensional network structure depending on short Cl…Cl contacts and hydrogen-bonding interactions. X-ray diffraction analysis revealed that 2 includes a butterfly-like bi-nuclear copper cluster unit with a Cl-bridge, [Cu(I)(bhmbpy)2(Cl)Cu(I)(bhmbpy)2]+, and forms a three-dimensional network structure depending on hydrogen-bonding interactions. [PW12O40]3– anions fill in the network based on hydrogen-bonding and electrostatic interactions. In them, the bhmbpy acts as a bidentate nitrogen donor ligand in the chelating fashion to coordinate with the Cu(II) center in 1 and the Cu(I) center in 2. The bhmbpy in 2 successfully constrains the Cu(I) within a rigid environment in a tetragonal-pyramidal geometry. The two compounds exhibit good proton conductivity (10−4 S·cm−1) at 100 °C in the relative humidity range 35–98%. Their luminescence behaviors in the solid state at room temperature have also been investigated. Upon excitation at 384 nm, 1 exhibits three emission peaks centered at 439, 507 and 566 nm. When excited at 364 nm, 2 displays three emission peaks centered at 443, 501 and 553 nm.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Haitao Yan,Didi Li,Zhaocong Jiang,Haoyuan Gu,Mengyuan Zhu,Yi-Fan Han,Minghui Zhu
Cu-based catalysts have been extensively used in the methanol steam reforming (MSR) reaction owing to low cost and high efficiency. In this work, we investigated the promotional effect of Fe on the Cu/ZnO/Al 2 O 3 catalysts prepared by an incipient-wetness impregnation method using a series of (quasi) in situ characterization techniques. The form of the Fe species was found to strongly depend on the Fe content. Fe species are present as highly dispersed FeO x in small amount of Fe with improved the dispersion of Cu. As Fe content increases, Fe species gradually transition to CuFe alloy and eventually to Fe 3 O 4 particles, leading to a decrease in Cu dispersion. With the gradual increase in Fe content, the apparent activity shows a volcanic trend, with CuAl-0.1Fe showing highest activity, whereas the intrinsic activity gradually decreases. Compared with CuAl- x Fe, adding moderate Fe to Cu/ZnO/Al 2 O 3 promotes the dispersion of Cu and Zn, forming abundant Cu-ZnO x interfacial sites, which improves both apparent and intrinsic activities. The best catalytic performance was obtained with the CuZnAl-0.1Fe catalyst, achieving the highest H 2 production rate of 134.7 mmol g cat −1 h −1 at 200 °C. This study reveals the role of Fe in Cu-based catalysts for MSR and inspires the design of improved Cu-based catalysts.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2021
·
IF 9.676
Ziyi Li,Haigang Hao,Jingjing Lu,Chengming Wu,Rui Gao,Jifan Li,Chun-Ling Liu,Wen-Sheng Dong
Here we exquisitely fabricated Cu/ZrO 2 -dp catalysts with plentiful Cu-ZrO 2 interfaces by depositing amorphous ZrO 2 onto Cu nanoparticles for the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). With the created plentiful Cu-ZrO 2 interfaces, the optimal catalyst 3Cu/ZrO 2 -dp exhibited exceptional catalytic performance under mild reaction conditions, and achieved the highest GVL mass productivity of 266.0 mmol GVL·h −1 ·g −1 Cu, which was 12.5 and 2.3 times of Cu/ZrO 2 catalysts with equivalent Cu loadings prepared by traditional impregnation (3Cu/ZrO 2 -im) or co-precipitation (3Cu/ZrO 2 -cp). As far as we know, this GVL mass productivity stood at the highest level compared with those obtained using non-noble metal catalysts under similar reaction conditions. By systematic investigation with multiple characterizations, density functional theory (DFT) calculations, and kinetic studies, it was found that interfacial active centers were created at Cu-ZrO 2 interfaces, which contained oxygen vacancies (O v ), negatively charged Cu δ− and partially reduced Zr 3+ . The O v favored the adsorption and activation of LA via its ketone group, while negatively charged Cu δ− was able to enhance heterolysis of H 2 , which resulted in the formation of H + -Cu δ− and Zr 3+ -H − active species via hydrogen spillover. Also, plentiful acid sites, which derived from coordinatively unsaturated and defective Zr species, generated at Cu-ZrO 2 interfaces. With the cooperation of interfacial active centers (Cu δ− -O v -Zr 3+ ) and acid sites, the fabricated 3Cu/ZrO 2 -dp with plentiful Cu-ZrO 2 interfaces achieved excellent catalytic performance for the hydrogenation of LA to GVL. Hence, the synergistic catalysis of Cu-ZrO 2 interfaces provided an effective strategy for designing catalysts with a satisfactory performance for the hydrogenation of LA, which also can be expanded to other hydrodeoxygenation reactions.
研究领域:
催化
·
化学工程
·
材料科学
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物理化学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2022
·
IF 9.136
Wen-Jian Yang,Li-Hui Yang,Han-Jun Peng,Si-Hao Lv,Hafiz Muhammad Adeel Sharif,Wei Sun,Wei Li,Cao Yang,Hui Lin
Electroreduction removal of nitrate (NO 3 – -N) is considered as a promising approach to solve its adverse effects on environment and human health, where efficient and cheap catalysts are required. Perovskite-based catalysts showed a versatile catalytic ability for wide range of redox reactions, but seldom applied for NO 3 – -N reduction. Herein, four perovskite oxide cathodes, LaMO 3-δ (M = Fe, Co, Ni and Cu) were prepared and used for the reduction of NO 3 – -N. The Ruddlesden-Popper (RP) type La 2 CuO 4 exhibited the best NO 3 – -N catalytic activity among the four perovskite oxide cathodes, with a removal rate of 11.7 × 10 -3 min −1 . The high selectivity of NH 4 + -N (82.4 ± 2.2%) indicated that NH 4 + -N was the main final product for NO 3 – -N electroreduction at La 2 CuO 4 cathode, but 100% of N 2 selectivity could be obtained with addition of 1000 and 1500 mg/L Cl - as the electro-assisted chlorination process. The mechanism of NO 3 – -N electroreduction occurred by both electron- and H*-mediated pathway, and the oxygen vacancies and redox cycle of Cu(I)-Cu(II)-Cu(I) were proposed as the accommodation sties and direct electron sources for NO 3 – -N reduction. Generally, this study opens a novel avenue for the development of earth-abundant, cost-effective catalyst with effective NO 3 – -N electroreduction.
研究领域:
环境科学
·
催化
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）