CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Jingyun Zhang,Zhen Jia,Shitao Yu,Shiwei Liu,Lu Li,Congxia Xie,Qiong Wu,Youzheng Zhang,Hailong Yu,Yuxiang Liu,Jinhui Pang,Yue Liu
Controllable carbonyl group (C O) hydrogenation is the key to the transformation of furfural molecules into high-value furfuryl alcohol chemicals. Herein, a non-noble copper metal catalyst (Cu/MgO) was prepared for the efficient hydrogenation of furfural to furfuryl alcohol under mild conditions. At 383 K and 2 MPa H 2 , 99.9% conversion of furfural with 99.9% selectivity to furfuryl alcohol was achieved within 80 min while the turnover frequency (TOF) was 56.87 h −1 . The temperature of a reductive pretreatment can be used to tune the nature of the interfaces between reduced copper and the metal oxides present in copper-magnesium oxide catalysts. The valence copper species exhibited unique catalytic properties in the hydrogenation of furfural to furfuryl alcohol. Besides, the Cu/MgO-350 exhibited excellent stability and reusability without significant activity loss. These results were accounted for by the MgO alkaline interface contributing to the effective formation and high dispersion of different valence Cu species. The active site had strong adaptability to the adsorption of reactants and desorption of products, thus avoiding excessive hydrogenation of furfural. According to the analysis of the characterization data, furfural adsorption mainly existed in η 1 (O)-aldehyde binding mode which was consistent with the density functional theory (DFT) calculation. DFT calculations of the reaction process showed that the theoretical results favored the hydrogenation of furfural through a hydroxyalkyl intermediate rather than of an alkoxide intermediate.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Yafei Qu,Wei Zheng,Peichen Wang,Hao Huang,Minxue Huang,Lin Hu,Hui Wang,Qianwang Chen
Electrochemical carbon dioxide reduction reaction (CO 2 RR) is an effective approach to capture CO 2 and convert it into value-added chemicals and fuels, thereby reducing excess CO 2 emissions. Recent reports have shown that copper-based catalysts exhibit excellent performance in converting CO 2 into multi-carbon compounds and hydrocarbons. However, the selectivity to the coupling products is poor. Therefore, tuning CO 2 -reduction selectivity toward C 2+ products over Cu-based catalyst is one of the most important issues in CO 2 RR. Herein, we prepare a nanosheet catalyst with interfaces of Cu 0 /Cu + . The catalyst achieves Faraday efficiency (FE) of C 2+ over 50% in a wide potential window between − 1.2 V to − 1.5 V versus reversible hydrogen electrode (vs. RHE). Moreover, the catalyst exhibits maximum FE of 44.5% and 58.9% towards C 2 H 4 and C 2+ , with a partial current density of 10.5 mA cm −2 at − 1.4 V. Density functional theory (DFT) calculations show that the interface of Cu 0 /Cu + facilitates C C coupling to form C 2+ products, while inhibits CO 2 conversion to C 1 products.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Chem
·
2024
·
IF 19.1
Xi Cao,Shan Ren,Xue Zhang,Qikui Fan,Qingqing Chen,Jian Yang,Junjie Mao
Cu-based catalysts are boosting electrocatalysts in CO 2 reduction reactions to high-value multicarbon (C 2+ ) products. Because of the unstable Cu + species and the unclear microscopic structure in reactions, Cu-based catalysts still face significant challenges of low selectivity and poor durability at high current density. Herein, we report a thermodynamically driven comproportionation strategy for forming a Cu 0 /Cu + /Cu 0 interface to stabilize Cu + species. When tested in a flow cell containing neutral electrolyte, the sample showed a high C 2+ products Faradaic efficiency (FE C2+ ) of 92.3% at a partial current density of 276.9 mA cm −2 . In a membrane electrode assembly, the sample achieved a 90.1% FE C2+ and maintained continuous operation for over 50 h at industrial current density. Further investigation demonstrates outstanding FE C2+ of >80% at a large industrial current of 10 A. Mechanism studies reveal that the Cu 0 /Cu + /Cu 0 interface lowers the energy barrier for C–C coupling in the reaction, thus facilitating the conversion of CO 2 to C 2+ products.
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2026
·
IF 9.2
Yanping Dong,Xiqiang Tian,Jinhui An,Pengyu Xu,Xinrui Wei,Muhammad Zahid
Achieving high activity, superior selectivity, and durable performance remains challenging for pristine MOFs in heterogeneous hydrogenation catalysis. Herein, nitrogen-doped carbon-wrapped Cu@Cu 2 O/NC heterogeneous catalysts enriched with Cu 0 –Cu + interfacial sites were readily derived by calcining Cu-MOF under an air atmosphere. Comprehensive characterization was conducted to examine synthesis-induced variations in bulk crystallinity, surface chemistry, and catalytic activity for Cu-MOF-250, Cu-MOF-350, and Cu-MOF-450. Compared to its counterparts, the Cu-MOF-350 catalyst exhibited optimal performance in the preferential hydrogenation of noxious 4-nitrophenol (4-NP) to valued 4-aminophenol (4-AP), maintaining high activity for up to ten consecutive rounds. The enhanced catalytic hydrogenation efficiency of the Cu-MOF-350 catalyst is ascribed to its distinctive nanostructural features, which originate from the synergistic interplay between Cu and Cu 2 O species. In addition, the improved uniform distribution of Cu@Cu 2 O nanoparticles generates higher concentration of interfacial exposed reactive Cu 0 /Cu + sites on the Cu-MOF-350 surface, which are considered crucial for the promoted hydrogenation of 4-NP.
✓ 已验证
DOI
高影响因子
ChemPhotoChem
·
2025
·
IF 3
Mengrong Zhang,Sha Ni,Zichao Yang,Min Zhang,Zhongjie Guan,Jianjun Yang
Graphical Cu-modified monoclinic TiO 2 nanoflowers with OVs (Cu 1 TB-1.5) promote the reactivity and selectivity of CO 2 reduction to CO under visible light. CO selectivity is 99.6%, and the cycling stability is excellent. The Cu 1 TB-1.5 facilitates the formation of the intermediate COOH* during the photocatalytic process, thus improving the yield and selectivity of CO. The photoreduction of CO 2 has attracted extensive attention as a promising solution to global warming. In this study, Cu-modified TiO 2 (B) (CuTB) nanoflowers with oxygen vacancies (OVs) are designed and synthesized via hydrothermal treatment and photodeposition to promote the reactivity and selectivity of CO 2 reduction to CO under visible light. The CO and CH 4 yields of sample Cu 1 TB-1.5 under visible light are 5.72 and 0.02 μmol g −1 h −1 , wherein the CO yield was 15.5 times that of sample TB; its selectivity is 99.6%, and the cycling stability is excellent. OVs can broaden the light absorption of TB to the visible light region, and Cu promotes photoinduced electron transfer from TB to the Cu species and act as an active center. The OVs and Cu can synergistically enhance charge separation, CO 2 adsorption, and CO 2 conversion. The Cu 1 TB-1.5 facilitates the formation of the intermediate COOH* during the photocatalytic process, thus improving the yield and selectivity of CO. This research provides a unique idea for the development of novel highly selective photocatalysts.
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Qian Wang,Zhi Yu,Junting Feng,Paolo Fornasiero,Yufei He,Dianqing Li
The production of biofuel 2,5-dimethylfuran (DMF) from an important biomass platform of 5-hydroxymethyl furfural (HMF) involves a complicated reaction pathway due to the competition of C═O hydrogenation and C–O hydrogenolysis; however, the dependence of formed intermediates and catalytic sites needs to be further identified. Herein, we constructed a highly efficient and selective Cu/ZnO-Al2O3 catalyst via reduction of a CuZnAl-layer double hydroxide (LDH) precursor, aimed for studying the effect of Cu0/Cu+ species on forming different intermediates and their synergetic promotional effect on HMF hydrodeoxygenation. As expected, the dependence of formation of different intermediates on the Cu+/Cu0 ratio was observed; notably, Cu/ZnO-Al2O3 with higher Cu+/Cu0 ratio finally gave 90.1% DMF selectivity at 100% HMF conversion, more selective than CuNi/Al2O3 (59.6%) and Cu/MgO-Al2O3 (75.8%) references. By a combined study of in situ IR experiments, the observed correlation between the reaction intermediates and the Cu0/Cu+ site suggests that Cu0 tends to adsorb the C═O bond as well as hydrogen molecule, while the Cu+ site is preferable to adsorb and activate the C–O bond. With the synergy of dual active sites, the Cu/ZnO-Al2O3 catalyst showed both high activity and selectivity to DMF. This work provides deep insight into the nature of active Cu species in multiple functional group biomass platform transformation.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Wen-Jing Yi,Jingyi Yang,Yongzhen Gao,Xiaotian Zhou,Wenlei Zhang,Meng Zhang,Zhongyi Liu
Copper catalysts have garnered considerable interest as promising active metals for upgrading biomass resources, especially in selective furfural (FF) hydrogenation reaction. However, effectively enhancing the interactions between active metals and supports while providing abundant surface reaction sites remains enormous challenge to improve catalytic performance. Herein, we present a unique hydrotalcite-derived Cu-based catalyst featuring well-dispersed Cu 0 /Cu + nanodots towards selectively hydrogenated FF to furfuryl alcohol (FA). Impressively, the optimized CuMg 3 Al-R catalyst exhibits the exceptional hydrogenation performance, achieving almost 100 % FF conversion and 99.3 % FA selectivity. Comprehensive studies reveal that the small sized Cu species with well dispersion, the synergistic effect of Cu 0 and Cu + , combined with the selective adsorption and activation of C O groups jointly contribute to the enhanced catalytic performance. This work offers a promising strategy to rationally design well-dispersed Cu species for the selective hydrogenation of C O groups, which holds great significance for biomass-related hydrogenation reaction.
✓ 已验证
产品关联
DOI
高影响因子
ChemSusChem
·
2026
·Vol. 19
·期 3
·e202502450
·
IF 5.9
Mengmeng Jin,Yaolei Zhao,Weiting Li,Tiantian Xu,Jiazuo Wei,Jingjun Liu
2,5-Bis(hydroxymethyl)furan (BHMF) is a promising intermediate for the synthesis of pharmaceuticals and crown ethers, whereas achieving a high reaction rate in the hydrogenation of 5-hydroxymethylfurfural (5-HMF) to form BHMF remains challenge. In this work, a series of Cu/CeO 2 –x catalysts ( x denotes H, Air, Ar) were synthesized by calcination under different atmospheres (10% H 2 /Ar, Air, Ar) and evaluated for the 5-HMF hydrogenation to BHMF. Cu/CeO 2 –Ar exhibited a superior reaction rate of 26.8 mmol·g cat −1 ·h −1 and BHMF yield of 99.1% under the condition (180°C, 5 h, 1 MPa H 2 ), significantly outperforming Cu/CeO 2 –H and Cu/CeO 2 –Air. The characterizations reveal that the calcination in the oxygen-deficient argon atmosphere led to high Cu dispersion and minimized Cu particle size in the Cu/CeO 2 –Ar. These properties resulted in the abundant Cu + –O V –Ce 3+ sites and increased Cu 0 number. In situ Fourier transform infrared spectroscopy analysis elucidates the distinct roles of these active sites. Cu + sites are responsible for perpendicular adsorption of the 5-HMF carbonyl group, and Cu 0 sites drive efficient H 2 dissociation. In contrast, the O V –Ce 3+ sites do not adsorb 5-HMF and H 2 . The close synergy between numerous Cu 0 sites and abundant Cu + sites in the Cu/CeO 2 –Ar accelerates the process of 5-HMF hydrogenation to BHMF. Graphical The oxygen-deficient argon atmosphere led to high dispersion and small particle size of Cu in Cu/CeO 2 –Ar. These properties resulted in the abundant Cu + sites for the adsorption of CO from 5-HMF and the numerous Cu 0 sites to efficiently dissociate H 2 , synergistically boosting catalytic reaction rate to 26.8 mmol·g cat -1 ·h -1 .
✓ 已验证
产品关联
DOI
PubMed
高影响因子
GREEN CHEMISTRY
·
2025
·
IF 9.2
Yahui Jiang,Haichuan He,Dan Xia,Hongwei Zhang,Shirui Tan,Li Luo,Yifan Kong,Liu Deng,You-Nian Liu
Cu-based catalysts are widely employed in the electrocatalytic CO2 reduction reaction (CO2RR) toward multi-carbon (C2+) products due to their unique electronic structures. However, Cu-based catalysts are prone to reconstruction under working conditions. Self-reduction and undesirable reconstruction have limited the activity and selectivity of these catalysts. Understanding their reconstruction behavior is crucial for elucidating reaction mechanisms and rationally designing catalysts. In this study, Br-doped Cu-base catalysts were employed to investigate the influence of dopants on catalyst surface reconstruction during CO2RR. Characterizations confirmed that during CO2RR, partial Br− leached from the precursor, while residual bromide ions in the Cu matrix created a bromine-rich environment on the catalyst surface, stabilizing Cu0/Cu+ active sites. The reconstructed catalyst exhibited superior selectivity for C2+ products and higher current density. In situ characterization and theoretical calculations demonstrated that the interaction between Br and Cu atoms suppressed complete Cu reduction. Furthermore, the asymmetric coupling pathway via *CO and *CHO intermediates dominated C2+ product formation, with significantly reduced Gibbs free energy of key intermediates compared to undoped CuO. Notably, halogen doping was validated as a universal strategy—Cu–Cl and Cu–F catalysts similarly enhanced C2+ production while exhibiting analogous reconstruction behavior. This study provided deep insights into catalyst surface reconstruction and offered effective strategies for designing high-performance catalysts for CO2RR.
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Shangpu Zhuang,Yilin Lei,Fan Xue,Tao Wei,Jiahui Chu,Mifen Cui,Zhuxiu Zhang,Ruiping Wei,Jihai Tang,Xu Qiao
Unraveling the synergistic interplay between Cu 0 /Cu + and support sites in Cu-based catalysts, coupled with oxygen vacancy-mediated active site modulation and their impact on hydrogenation performance metrics, remains a critical challenge in heterogeneous catalysis. Herein, we engineered a family of MOF-derived Cu/CeO 2 catalysts with tunable Cu loadings and oxygen vacancy(O V ) concentrations, featuring Cu 0 -Cu + -O V interfacial sites, through a MOF-mediated pyrolysis strategy. Operando DRIFTS, XPS, and Raman analyses revealed dynamic restructuring of active sites during hydrogenation of cyclohexyl acetate. The optimized catalyst achieved 98.0 % substrate conversion and 97.3 % cyclohexanol selectivity at 250 ℃ under 3 MPa H 2 , exhibiting a TOF 2.8-fold higher than conventional Cu/CeO 2 . The results indicate that the superior catalytic performance of Cu/CeO 2 -MOF should be attributed to the synergistic effects of Cu + , Cu 0 , and O V . This synergy enhances the ability of catalysts to adsorb and activate cyclohexanone, as well as its hydrogen dissociation capability. Further analysis indicates that O V exerts a direct influence on product selectivity. Moreover, the concentration of O V modulates the ratio of Cu + /(Cu + +Cu 0 ), which significantly affects conversion efficiency of the reaction. This work introduces an innovative approach to designing the electronic structure of copper-based catalysts, thereby optimizing the hydrogenation reactions of carbonyl compounds.
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2022
·Vol. 12
·期 19
·5879-5890
·
IF 6.177
Dengfeng Dai,Chao Feng,Minmin Wang,Qingzhou Du,Dandan Liu,Yuan Pan,Yunqi Liu
Biomass-based chemicals as a renewable alternative to petroleum-based chemicals are of great significance. The conversion of biomass-based furfuryl alcohol to pentanediol, including 1,5-pentanediol and 1,2-pentanediol, is explored over a series of bifunctional Cu/MFI catalysts in a continuous-flow reactor. These catalysts are synthesized by supporting copper nanoparticles on MFI zeolites with varying molar ratios of SiO2/Al2O3. Among them, the Z60-10Cu catalyst containing balanced Cu0–Cu+ and Brønsted acid sites exhibits excellent performance, and a high furfuryl alcohol conversion of 99.5% and selectivity of 85.2% for 1,5-pentanediol (69.2%) and 1,2-pentanediol (16.0%) could be achieved (hydrogen pressure: 2.5 MPa) at 160 °C. The experimental results and the results obtained using the DFT technique revealed that the high catalytic activity realized during the processes of ring-opening and hydrogenation could be attributed to the synergistic effect between the Cu species and Brønsted acid sites. The Brønsted acid sites on the Si(OH)Al groups significantly affect the ring-opening process of furfuryl alcohol. The methoxy group on furfuryl alcohol adsorbs on the Cu+ sites, and the hydrogenation saturation of the ring-opening intermediate is realized under the influence of the activated hydrogen units on the Cu0 sites. The results reported herein could help promote the continuous production of high value-added pentanediol from biomass-based raw materials in the presence of non-noble metal catalysts. An economical and feasible path for the transformation of biomass resources into high value-added fine chemicals could also be developed.
✓ 已验证
产品关联
DOI
高影响因子
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.
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）