Nanoscale
·
2024
·Vol. 16
·期 22
·10727-10736
·
IF 5.8
Peijiao Chen,Zhijun Li,Pengze Wang,Yuxin Yao,Tianwei Dou,Yang Qu,Liqiang Jing
The photocatalytic water-mediated CO2 reduction reaction, which holds great promise for the conversion of CO2 into valuable chemicals, is often hindered by inefficient separation of photogenerated charges and a lack of suitable catalytic sites. Herein, we have developed a glycerol coordination assembly approach to precisely control the distribution of atomically dispersed Cu species by occupying Ti-defects and adjusting the ratio between Cu species and Ti-defects in a hierarchical TiO2. The optimal sample demonstrates a ∼4-fold improvement in CO2-to-CO conversion compared to normal TiO2 nanoparticles. The high activity could be attributed to the Ti defects, which enhance the photogenerated charge separation and simultaneously facilitate the adsorption of water molecules, thereby promoting the water oxidation reaction. Moreover, by means of in situ EPR and FTIR spectra, we have demonstrated that Cu species can effectively capture photogenerated electrons and facilitate the adsorption of CO2, so as to catalyze the reduction of CO2. This work provides a strategy for the construction of atomic-level synergistic catalytic sites and the utilization of in situ techniques to reveal the underlying mechanism.
研究领域:
材料科学
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环境科学
·
化学
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Mengzhen Song,Jingru Han,Yingzhi Wang,Lungang Chen,YanYan Chen,Xiaoyuan Liao
Fe-based MOFs (Fe-MOFs) are deemed promising Fenton-like catalysts due to their well-developed pores and accessible active sites. However, their inferior catalytic activity, iron leaching, and low H2O2 utilization always hinder their application as Fe-based MOF catalysts. In this work, we manipulated the structure of Fe-oxo nodes in MIL-88B(Fe) via a CuI species substitution method, affording a mixed-valence (Cu-incorporated Fe-MOFs) with highly improved Fenton-like performance. It is found that the CuI serves as a shuttle to promote transfer between FeII/FeIII, inducing the formation of a larger amount of stable FeII sites, which was proven by experimental and DFT calculation results. A linear relationship was observed for the Fenton-like performance and the amount of CuI species for the catalysts. The corresponding value of the •OH formation is 2.17 eV for Cu-incorporated MIL-88B(Fe), which is significantly lower than that of MIL-88B(Fe) (2.69 eV). Meanwhile, the enriched CuI species suppress Fe species leaching during the catalytic reaction. The Fe-ion leakage of 0.4Cu@MIL-88B is very tiny (0.01–0.03 mg/L), significantly less than that of MIL-88B (2.00–3.02 mg/L). At the same time, H2O2 utilization for 0.4Cu@ MIL-88B(Fe) is 88%, which is almost 4.4 times that of pure MIL-88B(Fe). This work provides insights into the rational design of Fe-MOFs as promising Fenton-like catalysts for wastewater treatment.
研究领域:
环境科学
·
材料科学
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产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Wen-Jing Yi,Yongzhen Gao,Jingyi Yang,Xiaotian Zhou,Zhongyi Liu,Meng Zhang
A series of CuCoAl catalysts derived from layered double hydroxides (LDHs) with adjustable Cu/Co ratios were prepared via a facile in situ structure topotactic transformation strategy. The comprehensive characterization results revealed that the introduction of Co element and the confined effect of LDHs jointly promoted the dispersion and stability of Cu species, as well as significantly increased the active specific surface area. Interestingly, Cu 1.5 Co 1.5 Al sample showed the superior performance for furfural (FF) hydrogenation to furfuryl alcohol (FA) under the synergistic effect of Cu 0 and Cu + species, as well as the interaction between Cu species and the support. It allowed for FF conversion of 97.5% and FA selectivity of 99.7% (150 °C, 3 h, 2 MPa initial H 2 pressure, isopropanol as solvent, m(FF):m(catalyst) = 60:1). Moreover, Cu 1.5 Co 1.5 Al displayed the satisfactory reusability, where the activity and selectivity kept stable after six successive recycling runs. Specially, it displayed the promising potential for the scale-up production. Furthermore, the mechanism study based on in situ Fourier transform infrared spectra indicated that the surface exposed Cu 0 species could promote the H 2 adsorption and then rapidly dissociated H 2 into the activated H atoms, whilst Cu + species were the active sites for FF selective hydrogenation in a η 1 (O)-aldehyde adsorption configuration.
研究领域:
催化化学
·
材料科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Zhengting Xiao,Dongcai Shen,Kai Guo,Guangci Li,Wentai Wang,Xuebing Li,Song Chen,Chunhu Li
Cu-based catalysts were synthesized utilizing the ZnAl 2 O 4 spinel as supports for the selective hydrogenation of methyl stearate to stearyl alcohol. The presence of Zn atoms inhibited the agglomeration of the particles of Cu species in the reduction process, promoting the distribution of Cu species on the catalyst surface, which will enhance hydrogen activation and selective hydrogenation activity. DFT calculations show that the bond energies of the C-O bonds on both sides of the ester group decrease with the adsorption of the ester molecule onto Cu + species, and the C-O bond energy on the methyl side is lower than that on the carbonyl side. However, because the carbonyl carbon is more susceptible to nucleophilic attack, the C-O bond on the carbonyl side is more easily broken. In addition, the oxygen vacancies of the supports promote hydrogen spillover and the adsorption and activation of ester groups, which further enhance the selective hydrogenation activity of the catalyst on methyl stearate.
研究领域:
催化化学
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材料科学
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理论计算
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产品关联
DOI
高影响因子
JOURNAL OF POROUS MATERIALS
·
2021
·Vol. 29
·期 2
·371-380
·
IF 2.496
Zhang Wei,Xue Haonan,Wang Min,Wu Zeying,Ding Linlin,Deng Yaoyao,Wang Wei,Wei Xuejiao,Zhang Zhenwei,Xiang Mei
Cu-containing Beta zeolites (Cu-Beta) are straightforwardly synthesized in a one-pot method without template, where the crucial step is the co-hydrolysis/condensation of silica source and copper salt at the moderate acidic condition. In the solvent-free oxidation of cyclohexane with molecular oxygen (O 2 ), the best cyclohexane conversion result (9.7%) with a KA-oil (cyclohexanone and cyclohexanol) selectivity of 94.1% is obtained over Cu-Beta(100). Structure—activity relationship analysis indicates that the isolated tetrahedral framework Cu 2+ species and chemisorption oxygen species in high concentration on the catalyst surface enhannce the catalic performance. In addition, the catalyst can be easily separated and still remain stable after recycling five times, providing new insights into catalysts design for the catalytic oxidation of cyclohexane to KA-oil.
研究领域:
催化化学
·
材料科学
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产品关联
DOI
高影响因子
ChemCatChem
·
2018
·Vol. 11
·期 3
·1123-1130
·
IF 4.674
Xiao-Li Li,Guo-Hui Yang,Meng Zhang,Xiao-Feng Gao,Hong-Juan Xie,Yun-Xing Bai,Ying-Quan Wu,Jun-Xuan Pan,Yi-Sheng Tan
Graphical Tuning selectivity : Cu/SiO 2 was prepared by ammonia evaporation and used as catalyst for the direct synthesis of ethanol from CO hydrogenation. Both the Cu + /(Cu + +Cu 0 ) values and copper crystallite sizes had significant effects on the selectivity towards ethanol. Cu/SiO 2 catalyst was prepared by the ammonia evaporation method for the direct synthesis of ethanol from CO hydrogenation. The catalyst exhibited the initial ethanol selectivity as high as 40.0 wt %, which dramatically decreased from 40.0 to 9.6 wt % on the stream of 50 h. XRD, XPS, TEM and N 2 O titration techniques were employed to elucidate the ethanol selectivity change and catalyst structure evolution during reaction process. The experiment and characterization results indicated that both Cu + /(Cu + +Cu 0 ) value and copper crystallite size had great effects on the ethanol selectivity. During the initial 38 h, the ethanol selectivity obviously decreased from 40.0 to 18.2 wt %, and Cu + /(Cu + +Cu 0 ) value on the catalyst surface rapidly dropped from 0.67 to 0.39, while the copper crystallite size remained almost unchanged. However, during the reaction period of 38–50 h, the Cu + /(Cu + +Cu 0 ) value possessed no distinct change, but a further decrease in ethanol selectivity and a rapid aggregation in Cu particles were observed simultaneously. The present systematic investigation demonstrated that the decrease of Cu + /(Cu + +Cu 0 ) value was the main factor for the loss of ethanol selectivity during the initial 38 h, whereas the rapid growth of Cu particles during the reaction period of 38–50 h were mainly contributed to the further decline of ethanol selectivity.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
Small
·
2023
·Vol. 19
·期 40
·2303099
·
IF 13.3
Zi Yang,Deguang Ji,Zhi Li,Zidong He,Yang Hu,Jie Yin,Yichao Hou,Pinxian Xi,Chun-Hua Yan
Copper-based electrocatalysts effectively produce multicarbon (C 2+ ) compounds during the electrochemical CO 2 reduction (CO 2 RR). However, big challenges still remain because of the chemically unstable active sites. Here, cerium is used as a self-sacrificing agent to stabilize the Cu + of CuS, due to the facile Ce 3+ /Ce 4+ redox. CeO 2 -modified CuS nanoplates achieve high ethanol selectivity, with FE up to 54% and FE C2+ ≈ 75% in a flow cell. Moreover, in situ Raman spectroscopy and in situ Fourier-transform infrared spectroscopy indicate that the stable Cu + species promote C C coupling step under CO 2 RR. Density functional theory calculations further reveal that the stronger * CO adsorption and lower C C coupling energy, which is conducive to the selective generation of ethanol products. This work provides a facile strategy to convert CO 2 into ethanol by retaining Cu + species.
研究领域:
材料科学
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催化化学
·
能源转化
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产品关联
DOI
PubMed
高影响因子
CRYSTENGCOMM
·
2020
·Vol. 22
·期 23
·4005-4013
·
IF 3.117
Baolin Liu,Yizhao Li,Shaojun Qing,Kun Wang,Jing Xie,Yali Cao
Highly dispersed surface Cu species and oxygen vacancies are important for CuOx–CeO2 catalysts in many reactions, but it is difficult to increase the concentrations of highly dispersed Cu species and oxygen vacancies simultaneously by only adding a Cu component. Herein, CuOx–ZrO2–CeO2 (CZC) nanocatalysts with different ratios of Cu/Zr have been effectively produced by a simple solvent-free synthetic strategy. The effect of Zr doping on the structure and reactivity of the CuOx–CeO2 catalysts has been investigated with the help of carbon monoxide (CO) oxidation and 4-nitrophenol (4-NP) reduction as model reactions. It is revealed that the introduction of Zr relieved the agglomeration of surface Cu species, produced more oxygen vacancies in the interior and Cu+ species on the surface of the catalyst, and increased the reducibility of CuOx–CeO2. The CZC catalysts show remarkably enhanced catalytic activity due to the abundant surface active sites and the improved redox properties provided by the suitable doping of Zr into CuOx–CeO2. This work not only offers a practicable way to reconstruct the distribution of active metals on the metal oxide support but also provides a high-efficiency strategy to prepare oxide catalysts with excellent catalytic performance.
研究领域:
催化化学
·
材料科学
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DOI
高影响因子
Surfaces and Interfaces
·
2024
·
IF 5.7
Huiyu Tian,Haifeng En,Bingwen Li,Jinxian Zhao
An efficient Cu@C/SiO 2 catalyst for the hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) was prepared by sorbitol-modified ammonia evaporation method followed by calcination in N 2 . The Cu@C/SiO 2 catalyst exhibited the superior catalytic activity and stability for DMO hydrogenation compared with the Cu/SiO 2 catalyst. The optimized Cu@C/SiO 2 –1/4 catalyst exhibited an MG yield of 63 % during 90 h long-term evaluation under temperature of 210 °C, pressure of 1.9 MPa, WHSV of 1.25 g DMO ·g Cu -1 ·h -1 and H 2 /DMO of 150. The characterization results indicated that Cu dispersion can be significantly enhanced by the addition of an appropriate amount of sorbitol and the surface Cu 0 and Cu + species were effectively regulated by the amount of sorbitol. The catalytic activity of Cu@C/SiO 2 was linearly dependent on specific area of Cu + species under the sufficient specific area of Cu° for H 2 dissociation. In addition, the sorbitol–derived carbon species on the catalyst were also favorable for the enhanced stability owing to the suppression of Cu sintering.
研究领域:
催化化学
·
材料科学
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产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Jingjing Wang,Xinjie Wei,Zhihui Wen,Junjie Liao,Liping Chang,Jiancheng Wang,Kechang Xie
Ultra-deep desulfurization for the generation of clean petrol, diesel, and benzene remains a significant and challenging goal globally. Cu-containing materials have emerged as a promising desulfurization strategy due to their high adsorption capabilities. However, existing reduction technologies often lead to over-reduction. In this study, we reveal an intriguing and unexpected property of Y zeolite following ammonium ion exchange. The in situ generation of ammonia from ammonia pools may alter the location of copper species and modify their acid characteristics. We encapsulated various amounts of Cu into CuY zeolite, labelled as H-Cu X -Y(APE), using a facile self-reduction strategy. Notably, H-Cu 5.71 -Y(APE) exhibits an exceptional breakthrough sulfur capacity for thiophene, achieving 4.17 mg/g, nearly double that of traditional Cu-HY(H 2 ). XPS analysis following APE reduction indicates a high proportion of Cu + species in H-Cu 5.71 -Y(APE). In situ calcination FT-IR provided detailed insights into the chemical transformation of Cu 2+ species during APE reduction. Furthermore, CO-FTIR analysis shows that the Cu + content in the supercages of H-Cu 5.71 -Y(APE) reaches a maximum of 62.3 %. Py-FT-IR reveals the strong Brønsted acid content in H-Cu X -Y(APE) significantly increases. The desulfurization mechanism of H-Cu X -Y(APE) was thoroughly investigated using in situ FT-IR, demonstrating that the protonation and copolymerization of thiophene occurred on HCuY(APE) and could be effectively suppressed by adjusting the amount of copper. This work presents a promising solution for efficient ultra-deep desulfurization using an in situ NH 3 reduction method from ammonia pools.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Shengbin Dong,Man Wang,Hu Li,Hui Fu,Jie Yang,Minghui Zhu
Low-temperature catalytic oxidation has emerged as one of the most effective methods for removing carbon monoxide due to its economic feasibility. Copper-based (Cu-based) catalysts are increasingly regarded as viable alternatives to noble metal catalysts. While the incorporation of indium (In) into Cu-based catalysts has gained popularity, the impact of the In oxide (In2O3) phase on catalyst performance remains unclear. In this study, we prepared two different In2O3 with cubic (cb) and rhombohedral (rh) phases. Cu is supported on In2O3 via the impregnation method. The Cu/In2O3 catalyst with a cubic phase exhibited a higher CO oxidation activity (T90 = 122 °C). The primary reason for this enhanced activity is that the cubic phase of the In2O3 support promoted the generation of the surface Cu+ species. Based on the in situ DRIFTS results, Cu+ species and Cu+-CO species serve as active sites and active intermediates, respectively, in the CO oxidation reaction.
研究领域:
催化
·
材料科学
·
环境化学
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产品关联
DOI
高影响因子
Nanoscale
·
2023
·
IF 6.7
Xin Huang,Haitao Li,Bin Zhang,Yin Zhang,Hao Wang,Lijun Ban,Yixuan Xu,Yongxiang Zhao
It has been widely recognized that adjusting the size of Au particles has emerged as a significant approach in catalyst design, catalyst screening, and comprehension of reaction mechanisms. However, the essential factors of Au nanoparticles used only as an additive to enhance the activity of traditional multicomponent thermocatalysts have not been fully revealed. In this study, a series of Au@Cu2O core–shell nanocatalysts were synthesized through a controllable method, featuring core sizes ranging from 11 to 33 nm and an average shell thickness of approximately 55 nm. It was revealed that the size effect of Au cores plays a very vital role in the stability of the active Cu+ species under reducing atmospheres (H2, acetylene and formaldehyde) as well as the catalytic performance of the catalysts in the ethynylation of formaldehyde. The experimental findings revealed that Au@Cu2O core–shell catalysts with Au core sizes ranging from 11 to 16 nm exhibited a higher abundance of electron-deficient Cu+ species in the shell, which is attributed to the strong long-range electromagnetic effects of the Au core in the absence of photoexcitation or an applied electric field. Additionally, the active Cu+ species demonstrated remarkable stability under reducing atmospheres. Although the stability of Cu+ decreased slightly when the Au core size exceeded 16 nm, the Cu+ content remained above 80%. Notably, the Au@Cu2O catalysts with Au core sizes ranging from 11 to 16 nm exhibited excellent catalytic activity in the ethynylation of formaldehyde.
研究领域:
催化化学
·
材料科学
·
表面科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）