ACTA PHYSICO-CHIMICA SINICA
·
2025
·
IF 13.5
Lele Feng,Xueying Bai,Jifeng Pang,Hongchen Cao,Xiaoyan Liu,Wenhao Luo,Xiaofeng Yang,Pengfei Wu,Mingyuan Zheng
Ethanol dehydrogenation is a vital elementary step in ethanol upgrading, for which Cu-based alloy catalysts are the most promising candidates. Nevertheless, elucidating the underlying reasons for the synergistic effect between alloying components and host metals remains challenging due to the intrinsic structural complexity and dynamic evolution of alloy catalysts under operational conditions. Herein, single-atom Pd modified Cu-MFI catalysts with well-defined structures were designed for ethanol dehydrogenation to acetaldehyde and hydrogen. Comprehensive characterizations using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations revealed that Pd atoms are isolated by surrounding Cu atoms with a coordination number of 9–10, forming −0.36 e charged single-atom sites and being uniformly dispersed on the surface of Cu catalysts. The newly generated Pd δ − and Cu δ + sites synergistically reduced the activation energy barrier for C–H bond cleavage in ethanol. These sites simultaneously enhanced hydrogen adsorption and H–H bond coupling, leading to improved ethanol conversion and acetaldehyde productivity over Pt/Cu-MFI catalysts.
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MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING
·
2026
·
IF 5.2
Gui Chen,Yun-Hao Shao,Wen Zhu,Xin-Ping Qu
The oxidation of the Cu surface remains the most significant challenge of low-temperature Cu-Cu bonding technology. Schemes to achieve and maintain a high-quality Cu surface prior to bonding are therefore urgently needed. Co layer was used as a passivation layer and a simple wet treatment method using glycine was then proposed to remove surface oxides from Co metal. In this work, a novel simulated bonding methodology is proposed, which utilizes a two-step PVD Cu/Co on the PVD Co/Cu surface with a vacuum break, followed by annealing to simulate and investigate bonding mechanisms. The reliability of this methodology was first rigorously validated using Ar plasma activation as a benchmark, yielding simulated specific contact resistance results that closely align with actual bonding data. The simulation bonding methodology was employed to systematically optimize the process, after which the bonding mechanism was investigated. Consequently, chip-level bonding was successfully achieved at 230 °C, exhibiting an ultra-low specific contact resistance of 2.9 × 10 −8 Ω·cm 2 with a bonding area exceeding 99%. HRTEM and EDS analyses confirm that glycine treatment promotes direct Co-to-Co contact and uniform atomic interdiffusion. This methodology provides an efficient platform for investigating interfacial treatment processes and accelerating the development of advanced 3D integration technology.
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JOURNAL OF HAZARDOUS MATERIALS
·
2023
·
IF 13.6
Yuhang Zhang,Donglei Li,Liang She,Furong Guo,Falong Jia,Lizhi Zhang,Zhihui Ai,Xiao Liu
Heavy metal complexes in industrial wastewater are challenging to be removed by conventional methods arising from their stable chelating structure. In this study, zero-valent iron (ZVI) was ball-milled with tiny formic acid (FA), and the as-prepared sample (FA-ZVI bm ) was attempted to eliminate a model heavy metal complex of Cu(II)-ethylenediaminetetraacetic acid (Cu(II)-EDTA). The addition of FA to ball-milling could dramatically enhance the performance of ball-milled ZVI (ZVI bm ) towards Cu(II)-EDTA removal and increase the removal rate constant by 80 times. This conspicuous improvement of Cu(II)-EDTA elimination was attributed to the ferrous formate (Fe(HCOO) 2 ) shell formed on the surface of FA-ZVI bm . Results revealed that the Fe(HCOO) 2 shell facilitated the activation of O 2 to reactive oxygen species (ROS) and the leaching of Fe 3+ . Cu(II)-EDTA was decomplexed through both oxidative destruction and Fe 3+ replacement, and the released Cu 2+ was reduced by FA-ZVI bm and immobilized synchronously. Meanwhile, the ligands underwent oxidative degradation by ROS, thus avoiding the re-chelation ecological risk. Impressively, FA-ZVI bm could achieve cyclic treatment of actual copper complex wastewater and possessed promising advantage in treatment cost. This study would offer a promising approach for eliminating Cu(II)-EDTA through EDTA ligands degradation and synchronous Cu(II) removal, moreover to shed light on the decomplexation mechanism.
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PubMed
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CHEMOSPHERE
·
2023
·
IF 8.8
Huiwang Dai,Jingyi Zhu,Fanxu Meng,Daohui Lin,Wenjun Zhou,Dingjiang Chen,Ming Zhang,Qingqing Wang
In this study, Cu hybridization coupling oxygen defect engineering was adopted to synthesis of CuNiFe layered double oxides (CuNiFe-LDOs) in peroxymonosulfate (PMS) activation for degradation of methyl 4-hydroxybenzoate. The morphology and crystal structure of CuNiFe-LDOs was characterized in detail, which exhibited regular layered-structure at a Cu:Ni doping ratio of 1:1 and annealing temperature of 400 °C, and presented the crystal of Cu x O@Fe 3 O 4 –NiO. Besides, the X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) results demonstrated that abundant oxygen vacancies (OVs) and low oxidation state Cu species were composed in CuNiFe-LDOs400. The Cu 1·5 Ni 1·5 Fe 1 -LDOs400/PMS system showed excellent catalytic performance toward the degradation of butyl 4-hydroxybenzoate (BuP), and resistant to the effect of pH value and background inorganic anions. Based on quenching experiments and EPR measurements, singlet oxygen ( 1 O 2 ) was identified as the dominant active species during the heterogeneous catalytic process, which was generated by the synergistic interaction between OVs-Cu(I) site and PMS . In this process, the electron-drawing property of OVs promoted the adsorption of PMS molecule on Cu(I) site, followed by the accumulation of electron and cleavage of O–O bond to generate intermediate oxygen radical species, which donated one electron to eventually generate singlet oxygen.
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Catalysis Science & Technology
·
2020
·Vol. 10
·期 15
·5149-5162
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IF 5.721
Tongyang Song,Wei Chen,Yuanyuan Qi,Jiqing Lu,Peng Wu,Xiaohong Li
Achieving high catalytic performance with Cu-based catalysts is crucial for the hydrogenation of CO2-derived ethylene carbonate (EC) to simultaneously yield methanol (MeOH) and ethylene glycol (EG). Although Cu-based catalysts are widely studied for the target reaction, there are still some issues to be clarified. In this study, we prepared a 29.1 wt% Cu/SiO2-MHT catalyst by a modified hydrothermal method and successfully applied it to the hydrogenation of EC. In comparison with its three analogues having similar Cu loading and comparable Cu particle size but prepared by different methods, we found that the catalytic performance of the Cu/SiO2 catalysts, including the activity and the selectivity to MeOH, could be tuned by adjusting the Cu+/(Cu0 + Cu+) ratio via different preparation methods. As a result, the Cu/SiO2-MHT catalyst furnished 89% MeOH yield and 37.6 h−1 turnover frequency. To our best knowledge, these values are one of the highest among all heterogeneous Cu catalysts up to now. The results reveal that a cooperative effect exists between Cu0 and Cu+. When the Cu0 species are sufficient to activate H2, a more favorable formation of MeOH can be achieved with more Cu+ species and greater Cu+ surface areas. Furthermore, a greater amount of Lewis acid on the Cu/SiO2-MHT catalyst is also beneficial for MeOH formation.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Yanan Wang,Jiayu Ding,Qi Yin,Cheng Zhang,Yiqing Zeng,Song Xu,Qian Liang,Man Zhou,Zhongyu Li
This study developed a novel Cu@C/NCN-T composite for efficient photothermal catalytic CO 2 reduction. The composite, consisting of carbon-coated Cu (Cu@C) derived from Cu-BTC embedded in three-dimensional graphitic carbon nitride (NCN-T), was immobilized on the surface of carbonized wood (C-wood) floating on water, creating a triphase system (CO 2 , H 2 O, and catalyst). The optimized composite demonstrated remarkable CO 2 photothermal reduction performance, achieving a rate of 31.3 μmol·g −1 ·h −1 . This performance surpassed that of pure NCN-T and Cu@C by 1.6 and 3.8 times, respectively. The combination of Cu and carbon materials endowed Cu@C/NCN-T with excellent light-absorption properties, resulting in a photothermal effect that elevated the surface temperature and facilitated the catalytic reaction . Furthermore, the Schottky junction formed between Cu@C and NCN-T promoted the separation of electron-hole pairs, with Cu@C acting as charge channels. A charge transfer mechanism was proposed to explain these findings. This catalyst engineering approach holds promise for the development of efficient non-noble metal catalysts for rapid CO 2 photothermal reduction.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Yonglong Huang,Zhengkang Duan,Chuan Li,Tian Qiu
The catalytic dehydrogenation of diethanolamine to prepare iminodiacetic acid has attracted considerable research interest. However, the lack of understanding of the structure-activity relationship of the reaction can present a challenge to the control of the catalytic behavior. Concurrently, improving the catalytic performance and reducing the cost have also become urgent issues that require resolution. This work examined the catalytic mechanism of several Cu-Ni X /ZrO 2 catalysts, differing in Cu/Ni ratios, prepared by H 2 reduction, in the context of DEA dehydrogenation to elucidate the structure-activity connection and probable reaction mechanism. Subsequently, a strategy has been put out to generate metal (Ni and Co)-doped copper-zirconium catalysts using the co-precipitation-hydrazine hydrate reduction process. The synergistic effect between metals was combined with the improvement of the surface reaction of the catalyst by hydrazine hydrate through a more efficient preparation method, thereby enhancing the catalyst's overall performance. The representative catalyst Cu-Ni/ZrO 2 required a hydrazine hydrate reduction temperature and time of 40 °C and 30 min, and after 65 min of reaction, it exhibited a high conversion rate (96.3 %) and yield (93.7 %), and after five cycles, both the conversion rate and yield exceeded 85 %. Various characterization techniques have confirmed that Ni doping induced an alloying effect and a size effect. Additionally, the hydrazine hydrate reduction method was discovered to augment the specific surface area, surface hydroxyl groups, hydrophilicity, and optimize the pore size distribution of the catalyst while also regularizing its morphology, thereby significantly enhancing the activity and stability of the metal-doped copper-zirconium catalyst. This paper discussed the correlation between catalyst structure and reaction performance, as well as the catalytic conversion mechanism, which is anticipated to provide a novel reference for the preparation, performance control, and potential applications of dehydrogenation catalysts.
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Energy Storage Materials
·
2024
·
IF 18.9
Jing Peng,Bihua Hu,Zhitong Li,Xiongwei Zhong,Junwei Shi,Shuyu Cui,Xingzhu Wang,Baomin Xu
Dual-metal single-atom catalysts with heteronuclear active sites exhibit superior oxygen catalysis performance than their single-atom counterparts, facilitating the practical applications in advanced electrochemical energy devices. Herein, a Fe-Cu dual-metal single-atom catalyst with Fe-N 6 and Cu-N 1 S 2 coordination environment (FeCu-DSAs/NSC) is reported. Due to the synergism of bimetallic active sites and asymmetric heteroatom coordination, the resultant FeCu-DSAs/NSC displays better bifunctional catalytic performance (a small potential gap between the E η10 and E 1/2 , ΔE=0.647 V) when compared with the counterparts (Pt/C+IrO 2 and Cu-ISAs/NSC), as well as surpassing most of bifunctional metal atom-based catalysts reported to date. As expected, FeCu-DSAs/NSC based rechargeable zinc-air battery shows remarkable superiority than commercial Pt/C+IrO 2 benchmark, resulting in a high peak power density (230.66 mW cm −2 ), open-circuit voltage (1.464 V) and long-term cycling stability (up to 350 h at 10 mA cm −2 ).
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Peng Wang,Wei Nong,Yan Li,Hao Cui,Chengxin Wang
Although the electrochemical nitrogen reduction reaction (NRR) is regarded as a promising alternative to the Haber–Bosch process, it still suffers from the poor activity and low selectivity. Herein, we propose a powerful strategy to simultaneously boost the activity and selectivity by introducing strain engineering into the design of NRR electrocatalysts. The strain-engineered electrocatalysts consisted of monodisperse CuAu@Cu core-shell nanoparticles with controllable Cu skin via one-pot solvothermal process. Among them, electrocatalysts with about 2 layers of atomic Cu skin (CuAu@2LCS) achieve the highest NH 3 yield rate (33.9 μg NH3 h −1 mg cat. −1 ) and Faradic efficiency (24.1 %) at –0.2 V vs. RHE in 0.1 M HCl. Density functional theory (DFT) calculations reveal that owing to the unique structure of bimetallic alloys with the ultra-thin Cu skins, tensile strain and favorable ligand effect work together and tune the surface electronic structure of electrocatalysts, which not only strengthen N 2 affinity but also suppress the competitive HER process.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Zhiqun Xie,Jiali Zhou,Jinnan Wang,Corvini Philippe François-Xavier,Thomas Wintgens
Novel Fenton-like catalyst γ-Cu-Al 2 O 3 -Bi 12 O 15 Cl 6 with electron-poor Cu centre and electron-rich Bi centre was synthesized for selective degradation of phenolic compounds. Different from electron-rich Cu centre catalysts, the electron-poor Cu centre, which was induced by high electronegativity of Bi, could facilitate the formation of σ-Cu-ligand with phenolic compounds. On one hand, H 2 O 2 could directly oxidize σ-Cu-ligand to HO-adduct radicals with the generation of OH. Meanwhile, Cu(II) in the σ-Cu(II) complexes could be reduced to Cu(I) by oxidization of the HO-adduct radicals to hydroxylation products. Such reaction not only prevented Cu(II) from oxidizing H 2 O 2 to HO 2 /O 2 − but also enhanced the redox cycle of Cu(II)/Cu(I), which improved the catalytic activity and H 2 O 2 utilization. On the other hand, although the σ-Cu-ligand was gradually decreased with the decrease of phenolic compounds, dual-reaction centre played the dominant role in catalytic reaction . In addition, large amounts of oxygen vacancies (OVs) are formed in Bi 12 O 15 Cl 6 during the calcining process (BiOCl→Bi 12 O 15 Cl 6 ) , which can also increase the generation of OH. Thus, both electron-rich Bi center and OVs could still reduce H 2 O 2 to · OH for organics degradation even without the formation of σ-Cu-ligand. Being attributed to the synergistic effect of σ-Cu-ligand, dual-reaction centre and OVs mentioned above, γ-Cu-Al 2 O 3 -Bi 12 O 15 Cl 6 achieved high catalytic activity for phenolic compounds degradation and utilization efficiency of H 2 O 2 (η). In addition, various analytic methods (XPS, TPR, FT-IR, Raman, EPR and solid-state EPR) were used to prove the synergistic effect of the electron-poor/rich centre, σ-Cu-ligand and OVs of catalyst.
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Environmental Science-Nano
·
2024
·
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.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Yang Liu,Hailong Feng,Weiyi Li,Xueping Wang,Guoxiang Huang,Longxia Wang,Xingqiu Li,Yuxing Xie,Chenglu Liang
Catalysts in-situ reconstructed from transition metal sulfides for oxygen evolution reaction (OER) have been regarded as potential alternatives for the noble metal catalysts . Intriguingly, it was found that the self-optimized SO 4 2− @Cu doped Co(OH) 2 catalyst was reconstructed from bimetallic sulfide of CuCo 2 S 4 . During the OER process, the copper was partially leached and meantime doped into the in-situ generated Co(OH) 2 with SO 4 2− adsorption, while only oxides were discovered in counterparts of mono-metal sulfides. As a result, the SO 4 2− @Cu doped Co(OH) 2 catalyst exhibited superior OER performances, with low overpotentials of 211/272 mV to achieve the current densities of 10/100 mA cm −2 , exceeding the counterparts reconstructed from mono-metal sulfides. Experimental and theoretical results suggested that the in situ generated Cu doped Co(OH) 2 possessed thin and loosely layered structure with expanded lattice spacing (lattice spacing expanded from 0.28 nm to 0.46 nm) due to the SO 4 2− adsorption, making the intermediates more accessible to the active centers. In addition, the catalyst surface changed from hydrophobicity to super hydrophilicity , which greatly accelerated the mass transfer. This work indicated that the in-situ reconstruction process was greatly influenced by the interactions between metal sites and sulfide species, directly influencing the OER performances of the reconstructed catalysts.
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