Journal of Energy Chemistry
·
2025
·
IF 14.9
Jian Li,Jinzhi Jia,Zhongwei Wang,Huijiao Wang,Junfeng Huang,Yantao Wang,Wenhan Dai,Peng-an Chen,Jinhua Zhang,Mudong Tu,Hua Li,Haiyan Ma,Cailing Xu
Electrochemical nitrate reduction reaction (NO 3 RR) is a sustainable strategy to treat wastewater and produce ammonia. However, it is still a challenge to prepare electrocatalysts with high activity and selectivity. Herein, the CuO x nanowires supported Ru nanoclusters (Ru-CuO x ) were fabricated via a three-step procedure for efficient nitrate conversion and highly selective ammonia generation. The prepared Ru-CuO x shows a high ammonia yield rate of 2286.5 μg h −1 cm −2 at −0.7 V vs. RHE and Faradaic efficiency (FE) of 80.1% at −0.4 V vs. RHE. Additionally, the nitrate conversion rate exceeds 90% at the potential range from −0.2 to −0.7 V vs. RHE, and the ammonia selectivity can reach 97.7% at −0.7 V vs. RHE in 100 mg L −1 NaNO 3 solution. The systematic characterizations clarify that the introduction of Ru not only regulates the electronic structure of CuO x and accelerates the reconstruction of CuO x to Cu but also promotes H 2 O dissociation to generate active hydrogen. Moreover, in-situ Raman spectroscopy reveals that the formed Ru-Cu is considered the actual active species during the NO 3 RR. Density functional theory (DFT) calculations further prove that the obtained Ru-Cu facilitates the adsorption of nitrate and lowers the Gibbs free energy of the rate-determining step, thus improving the NO 3 RR performance.
研究领域:
电催化
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环境化学
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纳米材料科学
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能源化学
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表面科学
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可持续化学
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2023
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IF 9.9
Yiqing Li,Manqin Fu,Xiaoxia Zhang,Chun He,Dingsheng Chen,Ya Xiong,Liqing Guo,Shuanghong Tian
Highly reactive nanoclusters of metal oxides are extremely difficult to be synthesized due to their thermodynamic instability. For the first time, CuO x nanoclusters supported on anatase TiO 2 nanotubes (NT) with many defects as anchoring sites were successfully prepared. Although the copper loading reached as high as 2.5 %, the size of CuO x nanoclusters in the sample of 2.5 %CuO x /NT were mainly around 1.0 nm. The aggregation of copper species during the calcination process was undoubtedly hampered by the anchoring effects of the abundant defects in NT support. Due to the highly exposed undercoordinated atoms of CuO x nanoclusters, the mixed valences of copper, and the strong interface interaction between CuO x nanoclusters and NT support, 2.5 %CuO x /NT-catalyzed ozonation showed the highest pseudo-first-order reaction rate constant of 8.5 × 10 −2 min −1 , 2.2 and 4.0 times that of NT-catalyzed ozonation and ozonation alone, respectively. Finally, the catalytic mechanism was revealed by both experiments and density functional theory calculations (DFT). The results demonstrated that the undercoordinated Cu in CuO x /NT could highly promote the adsorption of ozone with a high adsorption energy of −125.16 eV and the adsorbed ozone was activated immediately, tending to dissociate into a O 2 molecule and a surface O atom. Thus, abundant reactive oxygen species , e.g., hydroxyl radical (·OH), superoxide radical (·O 2 – ) and singlet oxygen ( 1 O 2 ), could be generated via chain reactions. Especially, ·OH mainly contributed to the removal of ibuprofen pollutants. This work sheds a light on the design and preparation of highly reactive nanoclusters of metal oxide catalysts for catalytic ozonation of refractory organic pollutants .
研究领域:
催化
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环境科学
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材料科学
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化学工程
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产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Yanfei Liu,Zhang Liu,Chengxiong Wang,Jie Xu,Jianping Ai,Xiao Liu,Aimin Zhang,Yunkun Zhao,Chun Du,Bin Shan
Supported Pt catalysts suffer from low reaction selectivity (<65% at 100% conversion) in the selective catalytic oxidation of ammonia (NH3-SCO) because of their intrinsic over-oxidation tendencies. Herein, a strategy based on facilitating byproduct NOx reduction to N2 is demonstrated at CuOx/PtCu catalysts, aiming to tackle the low selectivity challenge. This PtCu alloy sample with a CuOx-rich surface displays an N2 selectivity of 95%, while its turnover frequencies are the highest among reported supported Pt-based catalysts. The enhanced reaction activities and N2 selectivities are primarily attributed to the Pt-Cuδ+ dual-site synergies at the CuOx/PtCu interface, in which dual sites exhibit distinct NH3 adsorption, activation, and dehydrogenation behaviors. The Olat assisted internal selective catalytic reduction mechanism at CuOx/PtCu with N2O22– as the central intermediates is proposed. Density functional theory calculation and temperature-programmed surface reaction measurements show that the N–O bond in N2O22– tends to break simultaneously with the assistance of Ov in CuOx followed by the easy transition from N2O22– to N2, which serve as the origin of the high selectivity.
研究领域:
催化化学
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环境科学
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材料科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2023
·
IF 15.1
Yaoyu Zhang,Yuxiong Wang,Yue Liu,Huimin Xu,Zhongbiao Wu
Pt@Cu-ZSM-5@CuO x catalyst was constructed for the catalytic oxidation of acetonitrile (AN), which achieved a complete mineralization rate and more than 95 % N 2 selectivity within 300–450 °C. Characterization results revealed that the satisfactory synergistic action of hydrolysis and oxidation pathways was well achieved. The NO x release from CN oxidation reaction on out-layer CuO x species and NH x species over-oxidation over Pt sites could be eliminated by NH 3 from CN hydrolysis reaction on Cu ions via internal selective catalytic reduction mechanism. The deep oxidation of carbon-containing intermediates (such as CO etc.) during CN decomposition over Cu species effectively occurred over Pt site. The encapsulation of Pt inner ZSM-5 zeolite not only strengthened low-temperature mineralization rate compared to Cu/ZSM-5 sample, but also inhibited NO x release caused by over-oxidation of AN at an elevated temperature with co-impregnation of Pt species over Cu/ZSM-5. This work provided a viable strategy for designing catalysts to effective abatement of NVOCs.
研究领域:
催化化学
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环境科学
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产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2024
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IF 7.4
Chao Yang,Xueying Zhao,Yunlong Zhao,Chenchen Ji,Ronglan Wu,Lu Wang,Xueqing Shao
CuO x -decorated TiO 2 (CuO x /TiO 2 ) nanoparticles have been prepared by the pyrolysis of Cu(II) complex on TiO 2 in an oxygen-limited atmosphere. A solution phase deposition method combined with freeze drying was employed for depositing the 2-methylimidazole-Cu(II) complex onto TiO 2 nanoparticles . The effect of decoration of CuO x on TiO 2 nanoparticles in terms of the crystal phase, morphology, chemical compositions , surface area , surface elemental states, optical absorption and emission properties, was investigated using a series of characterization tools. The oxygen-limited pyrolysis of 2-methylimidazole resulted in the reduction of partial Ti 4+ and Cu 2+ ions into Ti 3+ , Cu + and Cu 0 species, respectively. The surface decoration of CuO x was found to improve the separation and migration of photogenerated electron-hole pairs and increase the life time of excitons. Furthermore, the photocatalytic performance of CuO x /TiO 2 nanoparticles was evaluated for hydrogen evolution in aqueous methanol solution under UV–visible light irradiation . The CuO x /TiO 2 photocatalyst with the optimal cocatalyst loading achieved hydrogen evolution rate of 4.34 mmol h −1 g −1 , with 71- and 5.5-fold enhancement in activity over neat TiO 2 and CuO x /P25, respectively. It is expected that the combination of deposition and pyrolysis of 2-methylimidazole-Cu(II) complex could be an effective approach for the decoration of Cu and its oxides on other supports.
研究领域:
材料科学
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纳米技术
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光催化
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2018
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IF 4.521
Junmou Du,Huihuang Fang,Hongyan Qu,Jinping Zhang,Xinping Duan,Youzhu Yuan
5-Hydroxymethyl-2-furfural (HMF) is a key platform molecule for biomass utilization. The HMF derivative 2,5-furandicarboxylic acid (FDCA) by oxidation of HMF is a promising alternative for terephthalic acid as a monomer in polyethylene terephthalate. However, due to the facile purification of dimethyl furan-2,5-dicarboxylate (DMFD), an oxidative esterification derivative of HMF, is more desirable. In this work, supported Au–Cu bimetallic catalysts with Au–CuO x ( x = 0–1) nanohybrids were prepared by a reduction–oxidation pretreatment strategy. The as-prepared catalysts were used for the oxidative esterification of HMF into DMFD under base-free conditions using oxygen as sole oxidant. Activity tests showed that the optimized Au–Cu/γ-Al 2 O 3 catalyst displayed a remarkably high DMFD yield of up to 98% and a turnover frequency (TOF) value of 243 h –1 , whereas the monometallic Au and Cu catalysts exhibited poor performance. Various characterizations confirmed the strong interaction between Au nanoparticles and CuO x species, and their synergistic effect on the enhanced performance of HMF oxidative esterification. The reduction–oxidation pretreatment promoted the dispersion of CuO x and intensified the interaction of Au nanoparticles with CuO x . A plausible reaction mechanism for the oxidative esterification of HMF over Au–Cu/γ-Al 2 O 3 was proposed. This work provided new insights into the effect of reduction–oxidation pretreatment on the fabrication of supported Au–CuO x nanohybrids for the production of DMFD by HMF oxidative esterification.
研究领域:
化学工程
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催化科学
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生物质转化
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产品关联
DOI
高影响因子
Advanced Materials Technologies
·
2023
·Vol. 8
·期 22
·2301028
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IF 6.8
Liangliang Wu,Huajing Fang,Jiaqi Li,Lingqi Wu,Hong Wang
Viologen-based electrochromic devices have attracted great attention because of their tremendous potential in building energy conservation and low power display. However, the unsatisfactory performance at lower voltage limits their application, while the high driving voltage increases the energy consumption as well as safety risk. Herein, an electrocatalytic strategy is proposed for high-performance viologen-based electrochromic devices. Copper oxide (CuO x ) nanoparticles are uniformly deposited on the F-doped Tin Oxide (FTO) glass for enhancing the catalytic activity of Br − /Br 3 − redox couple, thereby promoting the interfacial charge transfer. The driving voltage can be reduced by ≈30% without sacrificing its high transparency (up to 80%) and the cycling stability can be significantly improved within 200 cycles. Large-area smart windows and electrochromic displays are fabricated, which can be driven by the 1.5 V dry battery. This work opens up a new path to optimize the electrochromic performance of viologens and also lays the foundation for the application of catalysis in optoelectronic devices.
研究领域:
材料科学
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能源技术
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光学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2023
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IF 9.5
Xuezhong Nie,Yehong Wang,Junju Mu,Jianyu Han,Huixiang Li,Nengchao Luo,Zhipeng Huang,Qiang Guo,Ning Li,Jian Zhang,Ning Li,Feng Wang
Nanoparticles exhibit unique catalytic performance, depending on their nanoscale size. However, controlling the particle size of the supported catalysts is still challenging. Here, we present a method for tunable redistribution of CuOx nanoparticles on rutile TiO2 support by physically adding pristine TiO2. The redistribution is driven by the work function difference (WFD) between the TiO2 support and the TiO2 additive, both of which exhibit distinct values, as determined through Kelvin probe force microscopy and electron binding energy analysis. Addition of TiO2 with lower work function (rutile) promotes electron transfer toward the CuOx/TiO2 composite, resulting in nanoparticle aggregation, while addition of TiO2 with higher work function (anatase) results in smaller CuOx on TiO2. The increase in particle size and electron density of CuOx, driven by the addition of rutile TiO2, promoted the complete conversion of nitrobenzene (100%) within 5 h. This is 2.7 times that of dispersed and degraded CuOx driven by mixing with anatase TiO2 (36.9%).
研究领域:
材料科学
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催化化学
✓ 已验证
DOI
高影响因子
ACTA PHYSICO-CHIMICA SINICA
·
2026
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IF 13.5
Miao Zhao,Qi Mao,Pengfei Zhang,Manyi Gao,Xuefei Zhao,Chunmei Ding,Can Li
With the advancement of industry and agriculture, substantial nitrate-containing pollutants have been discharged. This leads to severe environmental pollution and imbalance in nitrogen cycle, threatening ecology environment and human health. Electrocatalytic nitrate reduction to ammonia can convert pollutants into important chemical feedstocks and energy-storage molecules, providing a feasible route for ammonia production using renewable energy. However, this reaction is complicated and involves multiple steps and intermediates, suffering from high overpotential and limited selectivity and activity. To solve this issue, herein we designed a mixed-valence Cu/CuO x catalyst which is primarily composed of Cu and Cu 2 O and shows three-dimensional nanowire structure, achieving efficient nitrate reduction reaction for ammonia synthesis. The current density for ammonia production reaches 1.89 A·cm −2 at −0.22 V vs . RHE (reversible hydrogen electrode), with a Faradaic efficiency of 80.9%. Cu/CuO x also maintains excellent stability during prolonged electrolysis. The apparent and normalized performances of Cu/CuO x are much higher than those of the control systems, such as Cu and Cu 2 O. Experimental and theoretical results prove that the Cu 0 and Cu + species in Cu/CuO x play synergistic roles, promoting the conversion of *NO intermediate to *NOH and accelerating the desorption of NH 3 . The nanowire structure provides abundant active sites, thereby enhancing the performance of nitrate reduction to ammonia. This work not only provides an efficient catalyst for nitrate reduction to ammonia but also serves as a guideline for the rational design of such catalysts. Synergistic effect of Cu 0 and Cu + in Cu/CuO x nanowires enables efficient nitrate reduction to ammonia. Download: Download high-res image (261KB) Download: Download full-size image
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Anbang He,Yong Yang,Qiang Zhang,Ming Yang,Qian Zou,Jun Du,Changyuan Tao,Zuohua Liu
Electrochemical reduction of CO 2 to C2 products on Cu-based catalysts provides a promising approach for controlling the global carbon balance and restoring renewable surplus electricity. The enhanced CO 2 adsorption and CO local concentration are beneficial for CO 2 conversion and C2 intermediates formation, promoting the progress of CO 2 utilization. Here, we report a bimetallic MOF-derived Co 3 O 4 -CuO x /C (M-CuCo/C) catalyst constructed with Co 3 O 4 and CuO x sites wrapped in the carbon skeleton, achieving efficient CO 2 activation and C2 generation under low overpotential. The optimized M-CuCo/C catalyst (Cu/Co ratio of 1:2) exhibits a total current density of 19.28 mA/cm 2 at −1.05 (V vs. RHE), which is 8.60 times than that on MOF-derived CuO x /C (M-Cu/C). The highest C2 faradic efficiency (FE) reaches 79.2% (-0.75 V vs. RHE), accompany with a C2 production rate of 275.6 μmol/(g·h). The special nanorods-like morphology assembled by dual sites significantly increases electrochemical surface area and electron transmission rate during eCO 2 RR. The local CO intermediates under real-time electrochemical environment are monitored via rotation ring disk electrode (RRDE) techniques. Combined with in situ infrared measurements and DFT studies, it’s demonstrated that CO 2 could be efficiently converted to CO under low overpotential on Co 3 O 4 sites, forming local CO-enriched environment around neighboring CuO x sites and further accelerating the process of C2 formation.
研究领域:
化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Jianing Mao,Guanghui Feng,Xiao Dong,Ziran Xu,Bingbao Mei,Yiheng Wei,Xiaohu Liu,Guihua Li,Shoujie Li,Yanfang Song,Fei Song,Wei Wei,Wei Chen,Zheng Jiang
CH 4 , as an important clean fuel and hydrogen carrier, its production from CO 2 driven by renewable energy could simultaneously achieve energy supply, CO 2 emission reduction, and renewable energy consumption, which is of great significance. Electrocatalytic CH 4 production relies on high-valence Cu species for realizing multielectron reduction, while facing inadequate performance stability due to the reconstruction tendency of Cu. Herein, an amorphous CuO x -SiO 2 catalyst (amorCuO x -SiO 2 ) is synthesized via an electrostatic interaction strategy to construct stable Cu 2+ active sites for efficient electrocatalytic CH 4 production. AmorCuO x -SiO 2 shows a good reconstruction resistance during electroreduction, confirmed via X-ray absorption spectroscopy studies, endowing a 63.7% CH 4 faradaic efficiency at 500 mA cm −2 , which is 7.8 folds of crystalized CuO x -SiO 2 (crysCuO x -SiO 2 ). Theoretical calculations revealed that stable Cu 2+ active sites enhanced *CO adsorption and were more susceptible for further hydrogenation, thus promoting the CO 2 -to-CH 4 conversion. Our findings provide a feasible strategy for developing reconstruction-resistant electrocatalysts for advanced CH 4 production performance.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2024
·Vol. 14
·期 9
·578
·
IF 3.8
Yanmin Zhang,Yu Liu,Rui Zhao,Bin Lu,Xuan Wang,Hengshan Qiu
Copper-based catalysts are widely applied in catalytic CO conversion. Despite their importance in determining catalytic performance, the interaction of CO with different copper states has often been the subject of debate. Herein, we discuss the preparation of four different CuOxstates (namely, fully oxidized and reduced (O-573 and R-573, respectively) and 800 and 1000 K annealed (A-800 and A-1000, respectively)) through in situ treatments, comparing CO adsorption behaviors with vacuum-transmission IR spectroscopy. CO only weakly adsorbed on the A-1000 and R-573 surfaces, whereas it led to the creation of trace amounts of surface oxygen vacancies over the O-573 surface, providing adsorption sites for the subsequent CO. Meanwhile, the produced CO2re-adsorbed on the catalyst to form carbonate species. The reduction process was notably promoted over A-800 due to the presence of abundant surface oxygen vacancies, demonstrating the key role of Cuδ+in oxygen vacancies, rather than merely its chemical state, in dominating the interaction of CO with CuOx.
研究领域:
催化化学
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表面科学
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光谱学
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材料化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）