INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2021
·
IF 3.764
Xiaoling Hong,Qilu Yao,Jianjun Long,Xiugang Li,Xiangshu Chen,Zhang-Hui Lu
Hydrous hydrazine (N2H4·H2O) has great potential as a convenient and safe hydrogen source for fuel cells. Tremendous efforts have been made to develop economic and efficient metal catalysts for hydrogen evolution from N2H4·H2O, but it remains a huge challenge. Herein, for the first time, noble-metal-free CuNi nanoparticles (NPs) immobilized on lanthanum oxycarbonate/reduced graphene oxide nanocomposites (CuNi/La2O2CO3/rGO) were successfully fabricated through an impregnation-reduction approach. Well-dispersed and ultrafine CuNi alloy NPs (∼3.2 nm) can be easily anchored onto La2O2CO3/rGO, and the aggregation of metal NPs can be effectively avoided. Benefiting from the small metal NP size, the synergistic effect between Cu and Ni, and the strong metal–support interactions, the Cu0.5Ni0.5/La2O2CO3/rGO nanocomposites (NCs) exhibited remarkably improved catalytic activity and 100% H2 selectively toward N2H4 decomposition, outperforming Cu/La2O2CO3/rGO, Ni/La2O2CO3/rGO, CuNi/rGO, and CuNi/La2O2CO3. The total turnover frequency of Cu0.5Ni0.5/La2O2CO3/rGO catalyst reached up to 114.3 h–1 at 343 K, indicating that the Cu0.5Ni0.5/La2O2CO3/rGO is one of the most active noble-metal-free catalysts ever reported for the same reaction. The low-cost and outstanding catalytic activity of CuNi/La2O2CO3/rGO NCs improved the feasibility of using N2H4·H2O as a chemical hydrogen carrier and is expected to be applied in economic hydrogen-based fuel cells.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2023
·
IF 7.2
Pengxiao Liu,Yan Jia,Yao Ning,Xiaocheng Zhang,Shuhui Tian,Fan Yang,Weiyu Song,Ying Zhang
This study demonstrates the significant effect of incorporating inexpensive transition metal nanoparticles into metal-organic frameworks (MOFs) to improve their room-temperature hydrogen storage properties. Low-cost nanoparticles (Cu, Ni, and CuNi) were incorporated into UiO-66(Zr) via the double-solvent approach (DSA) plus chemical reduction processes. All composites exhibited higher hydrogen storage capacity compared to pure UiO-66 at both room temperature and 60 bar. Notably, the hydrogen spillover efficiency of CuNi nanoparticles loaded in UiO-66 was comparable to that of MOF adsorbents embedded with noble metals such as Pd and Pt. The hydrogen storage capacity of CuNi@UiO-66 was significantly increased from 0.20 wt% to 0.74 wt%. DFT calculations showed that the CuNi alloys facilitated the adsorption and dissociation of hydrogen molecules in comparison to the single metal nanoparticles , thus favoring the hydrogen spillover effect and improving the hydrogen storage performance. This work demonstrates the potential of designing MOF loaded with inexpensive metal nanoparticles for optimized room-temperature hydrogen storage.
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Molecular Catalysis
·
2023
·
IF 4.6
Qiaona Liu,Xin Han,An Qian,Xin Pu,Lei Ye,Pengpeng Liu,Fengqi Zhang,Jichang Liu
Developing noble-metal-free dual-metal single-atom catalysts with rich active accessible sites and excellent catalytic activity is very meaningful and challenging, especially for photocatalytic hydrogen production reaction, which can significantly reduce the cost of photocatalytic technology application while reducing the use of noble metals. Herein, a novel noble-metal-free dual CuNi single-atom modified ZnIn 2 S 4 (CuNi SA -ZIS) photocatalyst with high hydrogen production performance were successfully prepared by a hydrothermal method. The ZnIn 2 S 4 with a spherical nanoflower structure is composed of ultrathin nanosheets, and AC HDDAF-STEM results shows that CuNi bimetallic particles are uniformly distributed on the surface of ZnIn 2 S 4 nanosheets and exhibit atomic level dispersion, forming dual-metal single-atom structure. The optimized 1 wt% CuNi SA -ZIS photocatalyst with the Cu/Ni ratio of 1:1 shows the optimum H 2 evolution performance with a rate of up to 7844.7 μmol· g −1 · h −1 using triethanolamine as a sacrificial reagent, which is significantly improved compared to pristine ZIS, Cu-ZIS and Ni-ZIS samples under simulated sunlight. Electrochemical and spectroscopic characterization results demonstrated that the improved photocatalytic activity of CuNi SA -ZIS was mainly due to the addition of the dual CuNi single atoms with a synergistic effect served as a co-catalyst for ZnIn 2 S 4 photocatalysts, providing efficient active sites for hydrogen evolution while preventing the fast recombination of photo-generated electrons and holes. This study provides a valuable source of ideas for the design of effective noble-metal-free dual-metal single-atom catalysts.
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ELECTROCHIMICA ACTA
·
2026
·
IF 5.8
Longying Zhao,Jiayu Chen,Donglin Xiang,Mierban Dawuti,Laping He,Yuangen Wu,Han Tao
Residual organophosphorus pesticides (OPs) in food pose a severe threat to public health, necessitating simple and sensitive on-site analytical methods. In this study, a signal-off electrochemical sensing platform for OPs was constructed based on the OP-induced inhibition of silver deposition triggered by red kidney bean esterase (RKBE), coupled with the signal amplification of a CuNi dual-atom catalyst (CuNi-DAC). RKBE catalyzes the hydrolysis of α-naphthyl acetate to produce α-naphthol, which reduces Ag⁺ to Ag 0 deposited on the electrode. The electroactive Ag 0 undergoes oxidation to generate a prominent oxidation current, providing a sensitive sensing signal for detection. CuNi-DAC modification of the electrode accelerates charge transfer, provides more active sites, and effectively amplifies the sensing signal. Upon exposure to OPs, the activity of RKBE is inhibited, thereby suppressing the production of α-naphthol. This leads to a diminished Ag 0 generation and subsequent a weakened oxidation current. The decrease degree of current signal shows a positive correlation with pesticide concentration. Under optimized conditions, the fabricated sensing platform exhibits a good linear response range of 10 pmol/L-1000 pmol/L for fenthion with a low detection limit of 5.4 pmol/L. Spiked recoveries in cabbage and apple samples ranged from 93.3% to 108.5%, validating the sensing platform's practicality and reliability. This work offers a facile and cost-effective electrochemical sensing approach for on-site screening of OPs.
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Nanoscale
·
2026
·
IF 5.2
Fan Xie,Fan Xia,Zhangyao Xu,Han Han,Ziqi Wang,Qingda Zhu,Haochuan Chen,Fuchao Yan,Yifan Lian,Jingyu Sun,Jincan Zhang
Multilayer graphene (MLG) is an excellent protective material for engineering alloy in aqueous environments, owing to its high crystallinity and nm-scale thickness. However, achieving conformal deposition of high-quality MLG films on porous alloys without damaging their intricate microstructures remains a challenge. Herein, utilizing CuNi alloy with multiscale microstructures as surrogate models, we achieve conformal growth of high-quality, continuous, MLG films (thickness < 5 nm) without damaging the porous structures at a temperature of 700 °C, which is the lowest reported to date for defect-free graphene growth. This breakthrough is mainly attributed to the use of methanol as the carbon source and the favorable catalytic activity of the CuNi substrates. Electrochemical tests in a corrosive solution show that the graphene-skinned porous alloy exhibits a 14-fold reduction in corrosion current density and an 8-fold increase in charge transfer resistance compared to the bare substrate. Furthermore, complete conformal coverage of MLG films is successfully validated on bulk-porous CuNi alloy, along with comparable protective efficacy. This work thus provides a universal low-temperature growth strategy for MLG on alloys with diverse structural features, enabling their stable service in aqueous environments and thus holding promising applications in marine engineering and energy-related fields.
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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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Functional Materials Letters
·
2026
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IF 1
Ling Wu,Yang Yang,Guohua Ma,Baogang Guo,Hailong Hu
One-dimensional alloy nanowires exhibit substantial application potential in electrocatalysis owing to their high axial surface-to-volume ratio, exposed crystallographic facets, and excellent electrical conductivity that facilitates facile electrode integration. In this study, initial attempts to synthesize nanowires using oleylamine and cetyltrimethylammonium bromide (CTAB) invariably yielded substantial quantities of alloy nanoparticle byproducts, regardless of variations in CTAB concentration or other synthetic parameters. To address this challenge, we systematically investigated the effects of surfactant concentration, surfactant type, and ammonium salts on the competitive formation of CuNi nanowires versus byproduct nanoparticles in oleylamine-mediated reduction systems. This enabled the development of an inverse micelle method that significantly enhances nanowire yield. This approach employs surfactant-stabilized nonpolar oleylamine micelles as microreactors, wherein nanowire nuclei form exclusively within the micellar interior, while the inert polar external phase effectively suppresses extramicellar particle formation. As nucleation proceeds, precursor depletion inside the micelles establishes a concentration gradient that drives continuous influx of precursors from the polar external phase, sustaining the reaction. The size-confining nature of the micelles further directs anisotropic growth, ultimately yielding high-aspect-ratio alloy nanowires. The electrocatalytic performance of the as-synthesized nanowires toward methanol electrooxidation was subsequently evaluated in alkaline media. The nanowires exhibit a pronounced anodic peak at 1.7 V in 1.0 M methanol, achieving a peak current of 4.2 mA, which corresponds to a specific activity of 16.97 mA·cm −2 and a mass activity of 36.52 mA·mg −1 , thereby confirming their high efficiency for the methanol oxidation reaction (MOR). This study establishes rational design principles for micelle-directed nanowire growth and provides a scalable synthetic platform toward robust, platinum-free alloy nanocatalysts.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
·
IF 19.7
Wanyin Xu,Yuanhao Chen,Tianhe Gao,Zihan Wang,Wenkang Miao,Peng Wang,Qianqian Li
Successfully tailored a dual-site architecture comprising Cu + /Ni δ+ -O V -Ti and CuNi NPs on the ultra-small TiO 2 support-derived from MIL-125(Ti). • Deeply revealed the defect rich Cu + /Ni δ+ -O V -Ti site promotes CO 2 adsorption, while the CuNi NPs with electron redistribution facilitates H 2 adsorption and desorption of the product CO. • Significantly enhanced the RWGS reaction activity and sintering-resistance. Copper (Cu)-based catalysts hold promise for the reverse water-gas shift (RWGS) reaction because of their 100% selectivity toward CO. However, their low intrinsic activity, and deactivation caused by irreversible sintering during RWGS reaction remain persistent challenges. Herein, we report a pore adsorption strategy to simultaneously achieve electronic structure modulation and preserve microstructure stability during the RWGS reaction. Specifically, a MOF-derived TiO 2 -supported CuNi catalyst is constructed with dual active sites consisting of Cu + /Ni δ+ -O V -Ti sites and CuNi nanoparticles (NPs). The optimized catalytic performance achieves CO 2 conversion of 37.1% with CO selectivity of 99.9% and operates stably for 200 h at 450 ℃, placing its performance among the advanced Cu-based catalysts reported to date. Atomic/electronic structure characterization and density functional theory calculations demonstrate that Cu + /Ni δ+ -O V -Ti sites with enhanced charge redistribution capability promote CO 2 adsorption. The CuNi NP sites with electronic interaction enhance H 2 adsorption and moderate CO adsorption. This work provides a rational design strategy for highly active, selective and stable Cu-based RWGS catalysts. Download: Download high-res image (286KB) Download: Download full-size image Dual active sites consisting of Cu + /Ni δ+ -O V -Ti sites and CuNi NPs are constructed in the MOF-derived CuNi/TiO 2 catalyst, enabling electronic modulation and structural stabilization for enhanced RWGS reaction.
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
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2023
·
IF 6.1
Junshuai Zhang,Cui Du,Chen Zhou,Shengyang Yang
The production of hydrogen and benzaldehyde (BAD) by splitting benzyl alcohol (BA) through photocatalysts is one of the common methods of converting solar energy to chemical energy. Herein, a photocatalyst to achieve high efficiency in hydrogen production was fabricated by loading Cu-Ni bi-metal on the CdS nanorods as a carrier. The 20% Cu 1 Ni 1 /CdS composite catalyst was used for simultaneous photocatalyze H 2 production and BA oxidation to BAD under light with activities of 14.517 and 13.220 mmol g -1 h −1 , respectively, which is 8.7 times and 7.9 times higher than that of pure CdS . The high production efficiency can be mainly attributed to the synergistic effect of Cu-Ni bi-metal and the close contact between Cu-Ni and CdS interfaces. These microstructures enhance light absorption, effectively promote charge separation, and reduce the complexation of photogenerated electrons and holes. This work provides new ideas for the design of a cost-effective catalyst.
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C-Journal of Carbon Research
·
2026
·Vol. 12
·期 1
·
IF 4.3
Qi Qiang,Kezhi Li,Tianzhan Shen,Haibo Ouyang
The pantograph slider is a key friction component in high-speed train systems, and its performance directly affects the safety and efficiency of operation. In this study, Cf/C/CuNi composites with carbon fiber contents of 1 wt.%, 3 wt.%, 5 wt.%, and 7 wt.% were prepared by a solvothermal method combined with spark plasma sintering (SPS). The influence of carbon fiber content on the mechanical and friction properties of the composites was systematically studied. The results show that the flexural strength of the composites increases from 20.20 MPa to 38.45 MPa with an increase in the carbon fiber content. However, excessive carbon fiber content can lead to fiber agglomeration and interface defects, thereby reducing the friction stability and increasing the wear rate from 0.64 g/m3to 1.60 g/m3. A carbon fiber content of 1 wt.% helps to form a continuous lubricating film, resulting in a low and stable friction coefficient. This study provides valuable insights for the design and optimization of high-performance pantograph slider materials for high-speed railway applications.
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LANGMUIR
·
2026
·
IF 4.4
Bihui An,Mingkun Wu,Haoran You,Chenhao Zhang,Mengkui Tian
Electrochemical conversion of carbon dioxide (CO2) into syngas is an effective strategy for mitigating global warming and enabling carbon circularity. However, achieving a tunable and stable H2/CO ratio remains challenging due to the competitive adsorption and reaction kinetics of CO2 reduction and hydrogen evolution. Herein, a metal–organic framework-derived pyrolysis strategy constructs CuNi bimetallic nanoclusters on nitrogen-doped carbon (CuNi–NC), where Cu–Ni electronic interactions enable site-specific regulation of surface adsorption. The optimized Cu1Ni1–NC catalyst achieves a high FECO of 93.3% and a CO partial current density of −25.82 mA cm–2, with excellent stability over 28 h. Across a broad potential window from −0.51 to −0.81 V (vs RHE), CO-rich syngas with an H2/CO ratio around 0.37 is consistently produced. Furthermore, the syngas composition can be tuned by modulating the Cu/Ni ratio and applied potential, altering the relative contribution of CuNi active sites differing in electronic structure. Combined in situ attenuated total reflection Fourier transform infrared spectroscopy and density functional theory calculations reveal that Cu–Ni electronic synergy induces site-specific electronic modulation, optimizing the d-band center to stabilize *COOH intermediates and promote selective CO2-to-CO conversion. This work establishes a Cu–Ni bimetallic catalytic system for tunable syngas production and provides mechanistic insight into site-specific adsorption driven by electronic synergy.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Guolong Qiu,Wei He,Guangxu Yao,Chuanzhen Feng,Huijuan Zhang,Jinling Ma,Yu Wang
Development of non-noble metal-based electrocatalysts to enhance the performance of zinc-air batteries (ZABs) is of great significance, but it remains a formidable challenge due to their poor stability and activity. Herein, a bifunctional CuNi-TiO x /NCNFS electrocatalyst , featuring with electron-rich copper-nickel (CuNi) alloy nanoparticles anchored on titanium oxide/ N -doped carbon nanofibers (TiO x /NCNFS), is constructed by a dual-substrate loading strategy. The introduction of TiO x has led to a significant increase in the stability of the dual-substrate. The strong electronic interaction between CuNi and TiO x strengthens the anchoring of active metal sites, thus accelerating the electron transfer. Theoretical calculations unclose that NCNFS can regulate the charge distribution of TiO x , inducing the charge transfer from NCNFS → TiO x → CuNi, thereby reducing the d-band center of Cu and Ni, which is beneficial to the desorption of intermediate oxide species of the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Therefore, CuNi-TiO x /NCNFS delivers a remarkable bifunctional performance with a low OER overpotential of 258 mV at 10 mA cm −2 and an ORR half-wave potential of 0.85 V. When assembled into ZABs, CuNi-TiO x /NCNFS shows a low potential gap of 0.64 V, a higher power density of 149.6 mW cm −2 at 330 mA cm −2 , and an outstanding stability for 250 h at 5mA cm −2 . This study provides a novel approach by constructing dual-substrate to tune the electronic structure of active metal sites for efficient rechargeable ZABs.
研究领域:
材料科学
·
能源化学
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