PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2023
·Vol. 120
·期 10
·e2206619120
·
IF 11.1
Wencui Li,Zhi Li,Hang Zhang,Pengxiao Liu,Zean Xie,Weiyu Song,Baijun Liu,Zhen Zhao
Selective oxidation of methane to organic oxygenates over metal–organic frameworks (MOFs) catalysts at low temperature is a challenging topic in the field of C1 chemistry because of the inferior stability of MOFs. Modifying the surface of Cu-BTC via hydrophobic polydimethylsiloxane (PDMS) at 235 °C under vacuum not only can dramatically improve its catalytic cycle stability in a liquid phase but also generate coordinatively unsaturated Cu(I) sites, which significantly enhances the catalytic activity of Cu-BTC catalyst. The results of spectroscopy characterizations and theoretical calculation proved that the coordinatively unsaturated Cu(I) sites made H2O2 dissociative into •OH, which formed Cu(II)-O active species by combining with coordinatively unsaturated Cu(I) sites for activating the C−H bond of methane. The high productivity of C1 oxygenates (CH3OH and CH3OOH) of 10.67 mmol gcat.−1h−1 with super high selectivity of 99.6% to C1 oxygenates was achieved over Cu-BTC-P-235 catalyst, and the catalyst possessed excellent reusability.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2019
·
IF 8.355
Qian Ye,Hao Xu,Jing Zhang,Qingguo Wang,Peng Zhou,Yunqi Wang,Xue Huang,Xiaowei Huo,Chaorong Liu,Jinfeng Lu
This work presented a new strategy to activate peroxymonosulfate (PMS) by the addition of nano-zero-valent tungsten (nZVT) via accelerating the redox cycles of Cu(II)/Cu(I), which induce the consecutive generation of highly reactive oxygen species ultimately. The oxidation capacity of the nZVT/Cu(II)/PMS process and the detailed mechanisms of PMS activation were investigated with tetracycline (TC) as the targeted pollutant. Our results indicated that about 70% TC removal was obtained in the nZVT/Cu(II)/PMS system in 15 min with an initial pH of 4.6. In addition, hydroxyl radicals ( OH), sulfate radicals (SO 4 − ), and superoxide radicals ( O 2 − ) were identified as the reactive oxygen species (ROSs) attributed to rapid TC decomposition according to the quenching studies and EPR technology. The effective component that was responsible for PMS activation and ROSs generation was ascertained to be the resulting Cu(I), which derived from the direct reduction pathway driven by epigenetic low valence tungsten species and the indirect reduction pathway driven by active hydrogen atoms. Further, the presence of Cu(II) significantly accelerated the corrosion of the nZVT powders, leading to the accumulation of low valence tungsten species and the decrease in the mean diameter of the ZVT nanoparticles. There was no obvious change of the composition and structure between the original and residual nZVT powders, as evidenced by XPS and XRD analysis. The degradation process of TC included the cleavage of specific functional groups, the ring-opening reactions and the hydroxylation process. This study provided theoretical significance in applying zero-valent metals to activate PMS through a cupric/cuprous redox cycling mechanism.
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Catalysis Science & Technology
·
2019
·Vol. 9
·期 10
·2673-2681
·
IF 5.726
Bing Hu,Yazhi Yin,Zixin Zhong,Dengdeng Wu,Guoliang Liu,Xinlin Hong
Maximizing the Cu–ZnO interface is regarded as the best strategy to promote methanol synthesis activity over CuZn catalysts. Reducing the ZnO particle size can enhance the Cu–ZnO interaction, but its synthesis with a sub-5 nm size still remains a challenge. Moreover, the fabrication of an active powder catalyst with an inverse ZnO/Cu configuration is still very rare. In this work, we report a facile synthesis of inverse ZnO/Cu catalysts by direct calcination of Cu@ZIF-8 (zeolitic imidazolate framework-8). The particle size of ZnO and Cu can be tuned by changing the Cu loading as well as the calcination temperature. Importantly, inverse ZnO/Cu catalysts with sub-5 nm ZnO were obtained under gentle calcination at 623 K. In the CO2 hydrogenation reaction, the highest methanol synthesis activity reached 933 g kgcat−1 h−1 at 533 K and 4.5 MPa, with a high turnover frequency (TOF) of 0.013 s−1, over an optimized C2Z-623 catalyst, which exceeds the commercial CuZnAl catalyst (HiFuel R120, Johnson Matthey) and has ranked the top reported value over advanced CuZn catalysts under comparable conditions. Such excellent activity is attributed to the inverse structure of Cu particles covered by sub-5 nm ZnO, which promotes the intimate Cu–ZnO interface with enhanced SMSI. Moreover, we find that the methanol turnover frequency (TOF) monotonically increases with decreasing the particle size of ZnO as well as Cu. It is proposed that reducing the ZnO size favors the spillover of reducible ZnOx species onto the Cu surface while lowering the Cu size is responsible for the enhanced amount of exposed Cu steps for accommodating Zn species, both of which could facilitate the formation of Zn covered Cu steps as active sites for methanol synthesis.
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Journal of Materials Chemistry A
·
2014
·Vol. 3
·期 2
·600-607
·
IF 0
Hanxing Chen,Ming Wen,Zaidi Huang,Qingsheng Wu,Jiali Liu,Teng Tu
Highly active Cu@ZnO brush-like nanostructures have been successfully synthesized through the heteroepitaxial growth process of ZnO branched nanorods (NRs) based on Cu core nanowires (NWs), and used for the evaluation of selective catalytic degradation for polycyclic aromatic compounds. The resultant Cu@ZnO nanobrushes, with the main diameter of ∼500 nm, consist of Cu core NWs with diameter of ∼50 nm and outer ZnO branch NRs shells with thickness of ∼250 nm. The as-designed Cu@ZnO nanobrushes exhibit high performance for the selective catalytic degradation of polycyclic aromatic compounds. Nearly 90% conversion with the reaction rate constant (k) of 0.012 min−1 can be achieved for anthracene, while only about 50% and 10% conversions are shown for phenanthrene and naphthalene, respectively. Besides the highly efficient transportation of electrons, Cu NWs have strong capacity for oxygen activation which results in the gathering of negative charges and rich chemisorbed oxygen onto the surface, which is responsible for the high catalytic efficiency of Cu@ZnO nanobrushes toward the selective degradation of anthracene.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Zhuxu Xu,Adelakun Moses Erinomo,Zhenhua Dan,Fengxiang Qin,Hui Chang
Accurate and sensitive surface-enhanced Raman scattering (SERS) substrates are urgently demanded for the various analytic techniques. The SERS substrates with multimodal and gradient porous structure, utilized for the Rhodamine 6G (R6G) detection, have been designed and successfully fabricated from the thermal diffusion couples of Al and Cu foils via chemical dealloying. The structural inheritance of the initial microstructure of thermal diffusion couple precursors governs the formation of the final layer-by-layer gradient porous Cu with different characteristic pore sizes and morphology. An outmost surface layer of disordered lipstick-like porous structure on the SERS substrates enhances SERS effects as has been expected. The SERS activity of R6G Raman probes on gradient porous Cu is evaluated as a SERS enhancement factor of 6.63 × 10 12 and limit of detection of 2.10 × 10 −17 mol/L, higher than other porous SERS substrates. Meanwhile, the present SERS substrates are flexible and exhibit good bending properties due to the unreacted Cu layer as a supporting skeleton and other gradient porous Cu layers. The superior SERS performances are considered to result from the synergetic effects of the surface scattering of porous Cu rods and enhancements of the high electromagnetic fields between the small gaps between the nanopores.
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Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Ying Huang,Juan Lei,Baobao Bai,Xiaoli Ren,Lijun Cheng,Yu Cao,Shuang Wang,Jinping Li
Traditional powder catalysts are not suitable for industrial applications due to low utilization of active phase and easy sintering. Therefore, monolithic catalyst MCCF with good stability and water-resistance was designed for the catalytic oxidation of toluene-acetone mixture, in which amorphous MnO x derived via pyrolysis of Mn-MOFs loaded on copper foam (CF) and different transition layers were employed between MnO x and CF to regulate Cu-Mn interaction. The combined action of amorphous MnO x and the Cu-Mn strong interaction enhanced the catalytic degradation of toluene-acetone mixture. The existence of amorphous MnO x and the impacts of Cu-Mn interaction on weakening Mn-O bonds and stimulating reactive oxygen species were verified by various characterizations. Furthermore, the reaction pathways of toluene and acetone on catalyst MCCF were revealed as well as their interactions within the mixture.
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Carbon Energy
·
2025
·
IF 24.2
Mengmeng Ma,Runkang Lin,Kaige Huang,Shizhong Yue,Maohong Fan,Zhijie Wang,Shengchun Qu
Functionalization has emerged as a pivotal endeavor to tailor the surface properties of photocatalysts. We propose a facile amine functionalization strategy to establish a Cu−In−Zn−S (CIZS)/NiS x hybrid with covalent bonds using individual ethylenediamine (EDA) molecules. Our approach witnesses a remarkable photocatalytic hydrogen evolution (PHE) competence of 65.93 mmol g −1 h −1 driven by visible light, the highest value yielded by CIZS to date. X-ray absorption spectra of CIZS and density functional theory (DFT) calculations confirm the crucial amine N→Cu coordination after amine functionalization. The new emerging coordination via lone-pair electron donation profitably accesses the regulation of the coordination environment, electronic structures, and carrier behavior. Moreover, individual EDA molecule with two-terminal −NH 2 group serves as a molecular bridge to hybrid CIZS and NiS x cocatalyst via N→Cu and N→Ni coordination, favorably promoting efficient charge transport. This study provides advances in practical functionalizing photocatalysts.
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ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Minghan Wu,Siqi Hao,Linfeng Qi,Yu Shi,Wei Yang,Jingjing Bao,Min Du,Zhengyu Mo,Licheng Sun
Thermogalvanic cells (TGCs) are at the forefront of effective thermoelectric conversion methods, but the practical utilization of their integrated devices is hindered by the suboptimal performance of N-type TGCs. Herein, a novel redox couple of Cu/Cu(en)22+ is proposed to construct a liquid-state N-type TGC. The electrochemical reaction involving the Cu electrode, ethylenediamine (en), and their chelated compound Cu(en)22+ exhibits a significant reaction entropy change, resulting in an enhanced temperature coefficient (α). We reveal that the α of the Cu/Cu(en)22+-based TGC reaches 1.64 mV K–1. Furthermore, by optimizing the concentrations of Cu2+, ethylenediamine, and (NH4)2SO4 in the electrolyte, both α and normalized power density can be significantly improved, achieving values of 2.12 mV K–1 and 676 μW m–2 K–2, respectively. Moreover, by constructing a P–N junction with P-type and N-type TGC, we achieve a high potential of 121 mV under a temperature gradient of 35 K. This work expands the available redox couple options for N-type TGCs and offers a new pathway for efficient thermoelectric conversion.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2018
·
IF 3.141
Xiaofeng Dai,Wen Xu,Teng Zhang,Tao Wang
Copper nanoparticles (Cu NPs) are a potential material for conductive inks because of their low price, high conductivity, and high electromigration resistance. However, Cu NPs are prone to be oxidized in air, which is lethal to conductivity. In this work, we report on the self-reduction of Cu NPs which are synthesized by the thermal decomposition of copper formate (Cuf) using oleylamine (OAM) as the complexing ligand and stabilizing agent. Although the particle surface partially oxidized to Cu2O in air, the cuprous oxide could be reduced to copper during sintering, because of the release of H2 through the decomposition of OAM adsorbed on Cu NPs. This self-reduction ability without the help of additional reduction agent makes the Cu NPs a promising material for conductive inks. The feasibility to formulate conductive ink with the prepared Cu NPs is demonstrated.
研究领域:
材料科学
·
化学
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Green Energy & Environment
·
2022
·
IF 12.781
Bolin Wang,Chunxiao Jin,Shujuan Shao,Yuxue Yue,Yuteng Zhang,Saisai Wang,Renqin Chang,Haifeng Zhang,Jia Zhao,Xiaonian Li
Rational design of catalytic sites to activate the C C bond is of paramount importance to advance acetylene hydrochlorination. Herein, Cu sites with electron-rich and electron-deficient states were constructed by controlling the impregnation solutions. The π electrons flowing from acetylene to Cu site are facilitated over the electron-deficient Cu sites, achieving high activation of C C bond. The contradiction between the increased activation of acetylene required for enhanced catalytic activity and the resistance of Cu site to reduction by acetylene required for maintaining catalytic stability can be balanced by establishing strong interactions of Cu site with pyrrolic-N species. The catalytic activity displays a volcano shape scaling relationship as a function of Cu particle size. Tribasic copper chloride is concomitantly generated with the construction of electron-deficient Cu sites. The H–Cl bond of HCl can be activated over the tribasic copper chloride, accelerating the surface reaction of vinyl chloride production. This strategy of inducing electron deficiency provides new insight into the rational design of catalysts for the synthesis of vinyl chloride with a high catalytic performance.
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Journal of Materials Chemistry C
·
2018
·Vol. 6
·期 30
·8105-8114
·
IF 5.976
Ping Gao,Xiang-Ying Sun,Bin Liu,Hui-Ting Lian,Xin-Qiang Liu,Jiang-Shan Shen
Developing a catalyst with a uniform and well-defined crystal structure is very important to establish a catalytic sensing system with high efficiency. In this work, Cu-BTC metal–organic frameworks (MOFs) without a crystalline CuO or Cu2O phase were successfully synthesized by using a low temperature synthesis method, and the as-prepared Cu-BTC MOFs were found to have outstanding catalytic activity towards the traditional oxidase substrate, o-phenylenediamine (OPD), to generate a colored and fluorescent product. The results of the kinetics analysis revealed that the catalytic behavior of Cu-BTC MOFs towards OPD could well follow the typical Michaelis–Menten equation, indicative of a strong affinity between Cu-BTC MOFs and OPD. On the basis of these findings, taken together the condensation reaction between the –CHO group of formaldehyde and the –NH2 group of OPD to form Schiff base compounds, a novel Cu-BTC MOF-based catalytic sensing system for detecting gaseous formaldehyde could be successfully established.
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BIORESOURCE TECHNOLOGY
·
2019
·
IF 6.669
Liping Kong,Chunze Liu,Ji Gao,Yuanyuan Wang,Liyi Dai
The alcoholysis of Kraft lignin was catalyzed by bimetallic Ni-Cu supported on H-Beta, HZSM-5, MAS-7, MCM-41 and SAPO-11 zeolite materials in isopropanol solvent. Results showed that a higher bio-oil yield of 98.80 wt% and monomer yield of 50.83 wt% without obvious char were achieved at 330 °C for 3 h over Ni-Cu/H-Beta catalyst. Isopropanol was found to be more effective in H 2 generation and facilitated to the hydrodeoxygenation of lignin-derived phenolic compounds. Moreover, the composition of liquid products was also influenced by the acidity and pore structure of catalyst. The superior cycloalkanes yield was produced over Ni-Cu/H-Beta with larger pore size and more acidity. In contrast, a large number of cyclic ketones/alcohols and alkanes were obtained over other zeolites supported catalysts with smaller pore size and less acid content. Besides, the temperature, time and solvent effect on the lignin depolymerization were also researched.
研究领域:
化学工程
·
可再生资源转化
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