APPLIED CATALYSIS B-ENVIRONMENTAL
·
2026
·
IF 19.7
Zichen Song,Wenqian Wang,Jiantao Fu,Xiangbo Ma,Xiaolei Wang,Guiling Wang,Zhiyu Ren,Honggang Fu
Ligand-directed inheritance creates asymmetric Cu–N/Cu–O motifs for CO 2 reduction. • Symmetry-breaking preserves highly active Cu δ+ interfaces under dynamic conditions. • Dual-mode *CO adsorption (atop/bridge) effectively bypasses C 2+ scaling laws. • Optimized sites lower C–C coupling barriers while poisoning hydrogen evolution. • Achieved 82.2% C 2+ FE at 0.9 A cm −2 with stable 50 h ampere-scale electrolysis. The electrochemical CO 2 reduction reaction (ECR) to multi-carbon (C 2+ ) chemicals is intrinsically hindered by the rigid scaling relations and geometric homogeneity of pristine copper surfaces, which enforce a singular atop-type *CO intermediate. Herein, we implement a ligand-directed motif inheritance strategy to synthesize nitrogen-doped CuO (N-CuO) nanoparticles, uniquely characterized by asymmetric Cu–N/Cu–O lattice motifs. Under severe cathodic polarization, these robust Cu–N bonds structurally modulate the metallic reconstruction, preserving local non-metal coordination to sustain a highly active, mixed-valence Cu δ+ species. Operando spectroscopic and theoretical analyses reveal that this local structural asymmetry disrupts adsorption homogeneity, explicitly driving the spatial co-adsorption of bridge- and atop-type *CO intermediates. This dual-mode configuration bypasses conventional kinetic bottlenecks to drastically accelerate C–C dimerization. Consequently, the N-CuO catalyst delivers a record-level C 2+ Faradaic efficiency of 82.2% at an industrially relevant current density of 0.9 A cm −2 , exhibiting exceptional structural and catalytic stability over 50 h of continuous flow-cell operation. This work establishes atomic-scale lattice asymmetry as a decisive design principle for stabilizing active Cu δ+ species and steering multi-carbon electrosynthesis at practical reaction rates. Download: Download high-res image (301KB) Download: Download full-size image A ligand-directed motif inheritance strategy is developed to precisely integrate asymmetric Cu–N/Cu–O motifs within the CuO lattice. This local structural asymmetry enforces the *CO atop /*CO bridge dual-mode co-adsorption, bypassing conventional scaling relations to lower the C–C coupling barrier while suppressing HER. The catalyst delivers a state-of-the-art C 2+ Faradaic efficiency of 82.2% at an industrially relevant 0.9 A cm −2 .
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Nanoscale
·
2016
·Vol. 8
·期 22
·11602-11610
·
IF 7.76
Deqian Zeng,Pingyun Gong,Yuanzhi Chen,Qinfu Zhang,Qingshui Xie,Dong-Liang Peng
Metal–semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal–semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu–ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core–shell nanoparticles, nanopyramids and core–shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu–ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi–ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu–Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal–ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu–ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal–semiconductor hybrid nanocrystals with multifunctionalities.
研究领域:
材料科学
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纳米技术
·
化学工程
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CHEMICAL ENGINEERING JOURNAL
·
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.
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APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Mingji Xu,Xi Ran,Ruoli Chen,Maoshen Chen,Ruijuan Qi,Chengqin Dai,Chunhua Luo,Hui Peng,Hechun Lin
Gas sensors based on metal/metal oxide heterostructures have shown rapid advancements due to their excellent sensing performance. However, it is difficult to control the formation of Cu/CuO nanostructure due to the easy oxidation of copper and limits its sensing application. Herein, we reported the controlled oxidation of Cu superfine particles (SPs) to form Cu/CuO nanostructure via reducing CuO with monoethanolamine, oxidized with H 2 O 2 and then in-situ annealed at 250 °C. The organic residue generated during the reducing step plays a key role in controlling the oxidation of Cu SPs to form Cu/CuO nanostructure. The nanomaterial was used to fabricate gas sensor, which presents excellent p-type sensing performance to ethanol with good selectivity and a good linear relationship in the range of 1 to 100 ppm ethanol. The response to 100 ppm ethanol can be up to 99.40 under 200 °C operating temperature, and the response under 250 °C is 30.66 with the shorter response and recovery time of 214 s and 74 s, respectively. The sensing mechanism can be explained by the adsorption–desorption model. This study provides a promising strategy for the synthesis of Cu/CuO nanostructure and open a new avenue for the development of highly sensitive ethanol sensor.
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CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2022
·
IF 3.898
Hongbin Shi,Qing Liu,Xiaofeng Dai,Teng Zhang,Yuling Shi,Tao Wang
The bimetallic nanoparticles compositing of Ni-rich core and Cu-rich shell (Ni/Cu NPs) were successfully synthesized by a liquid-phase thermal decomposition method. The content of copper and nickel in Ni/Cu NPs was controllable by adjusting the ratio of two metal precursors, copper formate (Cuf) and nickel acetate tetrahydrate (Ni(OAc) 2 ∙4H 2 O). Ni/Cu NPs were further anchored on graphene oxide (GO) to prepare a magnetic composite catalyst, called Ni/Cu-GO. The dispersibility of Ni/Cu NPs in solution was enhanced by GO anchoring to prevent the sintering and aggregation during the reaction process, thereby ensuring the catalytic and cycling performance of the catalyst. The catalytic transfer hydrogenation (CTH) reaction of nitroaromatics was investigated when ammonia borane was used as the hydrogen source. Cu dominated the main catalytic role in the reaction, while Ni played a synergistic role of catalysis and providing magnetic properties for separation. The Ni 7 /Cu 3 -GO catalyst exhibited the best catalytic performance with the conversion and yield of 99% and 96%, respectively, when 2-methyl-5-nitrophenol was used as the substrate. The Ni 7 /Cu 3 -GO catalyst also exhibited excellent cyclic catalytic performance with the 5-amino-2-methylphenol yield of above 90% after six cycles. In addition, the Ni 7 /Cu 3 -GO catalyst could be quickly recycled by magnetic separation. Moreover, the Ni 7 /Cu 3 -GO catalyst showed good catalytic performance for halogen-containing nitroaromatics without dehalogenation.
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Nanomaterials
·
2020
·Vol. 10
·期 3
·509
·
IF 4.324
Shuzhen Zhou,Lihua Kang,Xuening Zhou,Zhu Xu,Mingyuan Zhu
Ethylene is an important chemical raw material and with the increasing consumption of petroleum resources, the production of ethylene through the calcium carbide acetylene route has important research significance. In this work, a series of bimetallic catalysts with different Cu/Ni molar ratios are prepared by co-impregnation method for the hydrogenation of calcium carbide acetylene to ethylene. The introduction of an appropriate amount of Cu effectively inhibits not only the formation of ethane and green oil, thus increasing the selectivity of ethylene, but also the formation of carbon deposits, which improves the stability of the catalyst. The ethylene selectivity of the Ni–Cu bimetallic catalyst increases from 45% to 63% compared with the Ni monometallic counterpart and the acetylene conversion still can reach 100% at the optimal conditions of 250 °C, 8000 mL·g−1·h−1and V(H2)/V(C2H2) = 3. X-ray diffraction and transmission electron microscopy confirmed that the metal particles were highly dispersed on the support, High-resolution transmission electron microscopy and H2-Temperature programmed reduction proved that there was an interaction between Ni and Cu, combined with X-ray photoelectron spectroscopy and density functional theory calculations results, Cu transferred electrons to Ni changed the Ni electron cloud density in NiCuxcatalysts, thus reducing the adsorption of acetylene and ethylene, which is favorable to ethylene selectivity.Keywords:Ni–Cu;calcium carbide acetylene;selective hydrogenation;ethylene
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ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Kaicheng Qian,Tong Wei,Xiaoqing Yan,Dongming Qi,Mingwu Tan,Renhong Li
Element doping is a viable strategy to regulate the metal–support interface for enhancing the catalytic performance of supported metal catalysts. Herein, Cu/ZnO:Cu-TH catalysts are prepared by immobilizing Cu nanoparticles (NPs) on ZnO nanorods featuring an adjustable oxygen vacancy, in which partial Cu atoms at the Cu–ZnO interface are incorporated into the ZnO lattice to form CuxZn1–xO species. Such Cu atom doping induces the creation of distinctive Cu–CuxZn1–xO interface sites and optimizes electron transfer from ZnO to Cu NPs, thereby achieving intermediate activation and ultimately endowing the catalyst with superior performance in reforming alkali-free formaldehyde (HCHO) into hydrogen at low temperatures. The Cu–CuxZn1–xO interface sites serve as pivotal centers for HCHO reforming, where the Cu sites and CuxZn1–xO sites selectively engage in the cleavage of C–H bonds in HCHO and O–H bonds in H2O, respectively. Meanwhile, the presence of oxygen vacancies bolsters the Cu–CuxZn1–xO sites in enhancing the adsorption of HCHO and H2O, further improving the activity. The Cu/ZnO:Cu-450H catalyst, distinguished by abundant Cu–CuxZn1–xO sites and a high concentration of oxygen vacancies, demonstrates optimal activity with TOF values of 16.9 and 72.4 h–1 under anaerobic and aerobic conditions, respectively, which are 8.9 and 29.0 times higher than those of the Cu/ZnO-450N catalyst, which lacks doped Cu atoms and oxygen vacancies.
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Advanced Science
·
2024
·
IF 14.3
Jin Li,Qiuling Jiang,Xiujing Xing,Cuilian Sun,Ying Wang,Zhijian Wu,Wei Xiong,Hao Li
Electrochemical conversion of nitrate (NO 3 − ) to ammonia (NH 3 ) is a potential way to produce green NH 3 and remediate the nitrogen cycle. In this paper, an efficient catalyst of spherical CuO made by stacking small particles with oxygen-rich vacancies is reported. The NH 3 yield and Faraday efficiency are 15.53 mg h −1 mg cat −1 and 90.69%, respectively, in a neutral electrolyte at a voltage of -0.80 V (vs. reversible hydrogen electrode). The high activity of the electrodes results from changes in the phase and structure during electrochemical reduction. Structurally, there is a shift from a spherical structure with dense accumulation of small particles to a layered network structure with uniform distribution of small particles stacked on top of each other, thus exposing more active sites. Furthermore, in terms of phase, the electrode transitions from CuO to Cu/Cu(OH) 2 . Density functional theory calculations showed that Cu(OH) 2 formation enhances NO 3 - adsorption. Meanwhile, the Cu(OH) 2 can inhibit the competing hydrogen evolution reaction, while the formation of Cu (111) crystal surfaces facilitates the hydrogenation reaction. The synergistic effect between the two promotes the NO 3 - to NH 3 . Therefore, this study provides a new idea and direction for Cu-based oxides in electrocatalytic NH 3 production.
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JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY
·
2020
·Vol. 20
·期 3
·1660-1669
·
IF 1.134
Deng Yu-Ying,Xiao Xin-Feng,Wang Dan,Han Bo,Gao Yu,Xue Jian-Liang
Cu-BTC was synthesised by hydrothermal method in this study to adsorb and remove the toxic heavy metal hexavalent chromium Cr(VI) in water. The EDTA-chitosan/Cu-BTC was prepared by the surface modification of Cu-BTC with EDTA-modified chitosan. The initial concentration effects of adsorbed
chromium solution, adsorbent dosage, adsorption time, adsorption temperature and pH of chromium solution on adsorption capacity were estimated using the single-factor optimisation experiment. Results show that the adsorption capacity of the modified composite was higher than that of Cu-BTC.
Cu-BTC and EDTA-chitosan/Cu-BTC exhibited significant adsorption of Cr(VI) under acidic conditions in water and basically independent of temperature. Their adsorption processes conformed with the pseudo-second-order model. The Langmuir adsorption isotherm model obtained the adsorption isotherm,
which indicated that the adsorption process was single molecule adsorption. Isotherm fitting obtained the maximum adsorption amounts of Cr(VI) for Cu-BTC and EDTA-chitosan/Cu-BTC at 27.32 and 46.51 mg·g-1, respectively. Factor and principal component analyses show that the
main factors affecting the adsorption of Cr(VI) in the EDTA-chitosan/Cu-BTC composites are pH, initial concentration and adsorption time. Therefore, EDTA-chitosan-modified Cu-BTC was a more feasible metal-organic framework material than Cu-BTC because of better adsorption performance, which
can be used for adsorption removal of Cr(VI) in water.
研究领域:
环境科学
·
材料科学
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SENSORS AND ACTUATORS B-CHEMICAL
·
2021
·
IF 7.46
Jialing Zhou,Hui Huang,Shunji Chen,Mengyuan Wang,Danna Zhao,Jun Yu,Senlin Jin,Yuan Zhong,Xiaoming Chen,Xiaocai Yu,Pengbo Liu,Jian Zhao
As 3rd generation semiconductor, GaN material is promising for biosensor application, owing to its excellent chemical stability and high carrier mobility. Herein, GaN porous-layer (GNP) was self-assembly grown on GaN-coated sapphire substrate without doping by using simple low-temperature (LT) growth. The GNP with a pore density as high as ∼2.1 × 10 3 μm −2 can be realized by optimizing the growth temperature (620 °C) and layer thickness (22.4 nm), and its normalized conductivity can be tuned by simply changing the thickness. The optimized GNP was applied to chemiresistive detection of Cu 2+ with a limit of detection (LOD) as low as 8 fM, a fast response speed of 1.5 min, a wide linear range (8 fM∼8 nM) and good repeatability. The LOD was improved 1.25∼10 6 fold compared with that of previously reported biosensor. The GNP biosensor features high sensitivity, simple structure, integratability, and low-cost. To our knowledge, it is the first time that GaN material was used for chemiresistive biosensor.
研究领域:
材料科学
·
生物传感技术
·
纳米技术
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CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Zhi Xu,Zi-He Meng,Song-Hai Wu,Shi-Jie Wang,Peng-Yue Zhu,Yong Liu,Hai-Tao Ren,Shao-Yi Jia,Xu Han
Sulfate radical (SO 4 •− ) is always thought to be an important oxidizing species in the metal-sulfite [S(IV)] systems, however, the oxidizing species correlated with the metal species have rarely been mentioned. In this study, the oxidizing species that oxidize arsenite [As(III)] in the Cu(II)-S(IV) system were investigated under alkaline conditions. Kinetic results indicate that complexation between Cu(II) and S(IV) is the pre-requisite to initiate various oxidizing species, followed by internal electron transfer from S(IV) to Cu(II) with the formation of SO 3 •− and the Cu I (SO 3 ) n −2n+1 complexes. Quenching experiments rule out contributions of SO 5 •− , peroxymonosulfate (HSO 5 − , PMS), hydroxyl radical ( • OH), superoxide radical (O 2 •− ) and singlet oxygen ( 1 O 2 ) to As(III) oxidation in the Cu(II)-S(IV) system and indicate that some kinds of peroxo species contribute. On the other side, apart from the oxidizing species such as SO 5 •− , PMS and SO 4 •− generated via a series of reactions between SO 3 •− and O 2 , the Cu I (SO 3 ) n −2n+1 complexes also react with O 2 to form Cu II -O 2 •− -(SO 3 2− ) n superoxo species and Cu III -O 2 2− -(SO 3 2− ) n peroxo species, as revealed by Raman analysis. UV–vis spectrum further confirms the presence of Cu(III) in the Cu(II)-S(IV) system. We therefore suggest that both SO 4 •− and the Cu(III)-peroxo species play important roles in the oxidation of As(III) in the Cu(II)-S(IV) system. This study enriches our understanding on the diversity of oxidizing species in the metal-S(IV) systems under alkaline conditions.
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ANALYTICA CHIMICA ACTA
·
2026
·
IF 6.1
Chengcheng Qi,Yaqi Kong,Juan Chai,Ziyin Yang
The size effect has a significant impact on the catalytic performance of metal nanostructures, where smaller sizes often correspond to higher specific surface area and specific activity. This study investigates the pyrolysis-temperature-dependent evolution of Cu-MOFs and reveals an anomalous size effect of Cu nanoparticles in glucose electrooxidation. Although low-temperature pyrolysis produces small Cu nanoparticles, the high-temperature pyrolysis product demonstrates exceptional performance despite the larger size of its Cu nanoparticles. The sensor based on larger Cu nanoparticles exhibits 24-fold higher sensitivity compared to small Cu nanoparticles. In-depth study reveals that high-temperature pyrolysis not only produces large-sized Cu nanoparticles but also induces and promotes the formation of oxygen-coordinated Cu single atoms. The coexistence of oxygen-coordinated Cu single atoms electronically modulates adjacent Cu nanoparticles via charge transfer, which accelerates the electron transfer rate and promots the generation of highly active sites at lower operating potentials, thereby overriding conventional size-activity constraints. This study not only highlights the non-negligible role of oxygen-coordinated metal single atoms during high-temperature pyrolysis and provides a new perspective to explain the anomalous size effect, but also redefines sensing materials design principles through single atom-nanoparticle interactions.
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