APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Zesheng Deng,Songchang Hu,Jiahui Ji,Shiqun Wu,Haijiao Xie,Mingyang Xing,Jinlong Zhang
Cu is widely used to prepare high-value products in photocatalytic CO 2 reduction reaction (CO2PR). The valence state of transition metals usually has a great impact on the catalytic process. However, the research on Cu valence in CO2PR is lack for its complex valence change. In current work, Cu x /P25 with stable Cu valence composition in CO2PR is prepared. The results show that Cu is composed of Cu 0 and Cu 2 O, and their proportions change regularly as Cu loading changing, which are linearly related to the selectivity of the corresponding products of CO2PR. Combined with thermodynamic and kinetic analysis, the CO adsorption and activation on the surface of Cu 0 and Cu 2 O are considered to be the key to determine the product of CO2PR, which is further confirmed by DFT calculation. Cu 0 and Cu 2 O are proved to be active site of producing CH 4 and CO, respectively. In this case, a reference for the study of highly selectivity Cu based photocatalysts is provided.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Jing Ding,Chenhui Qiu,Zhiqiang Zhang,Qinghua Qu,Cheng Fang,Jinfeng Zhang,Guofeng Guan,Hui Wan
Manipulating the oxidation states of transition metals is an ideal solution to achieve selective generation of different products and copper is widely used in CO 2 photocatalytic reduction to methanol. However, the understanding on the effects of valence states of copper species in SrTiO 3 on its structure and the selectivity of the corresponding product in CO 2 photocatalysis are currently still limited. Here, copper-doped SrTiO 3 nanofibers with different controllable ratios of Cu + /Cu 2+ and Cu + /Cu 0 were prepared by the combination of the electrospinning with the in-situ reduction method. The proportion of copper with different valence states (Cu + /Cu 2+ and Cu + /Cu 0 ) was changed by rationally adjusting the time of hydrogen reduction. The presence of monovalent copper facilitated the generation of reactive intermediates, thereby enhancing its photocatalytic activity. The copper-doped SrTiO 3 nanofibers obtained after 3 h of hydrogen reduction (STCu 0.08 -H-3 h) had the highest proportion of Cu + /Cu 2+ and Cu + /Cu 0 with the highest methanol yield (6.96 μmol·g −1 ·h −1 ). Methanol generation rate and Cu + /Cu 2+ ratio of STCu 0.08 -H-xh (x = 1, 2, 3, 4,5) with different hydrogen reduction time were proven to be linearly positively correlated. Furthermore, theoretical investigation and in-situ CO 2 infrared spectrum deeply understood the difference of CO 2 adsorption behavior and CO 2 activation over Cu 2+ and Cu + of STCu 0.08 -H-3 h photocatalyst and the reaction intermediates involved in the photocatalytic CO 2 reduction to methanol.
研究领域:
材料科学
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环境科学
·
化学工程
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2025
·
IF 8.3
Lingwei Yu,Leyi Zhou,Qi Guo,Hongchuan Zhang,Xi Xiao,Ruixue Zhao,Zifeng Yan,Ying Zhang
The challenge of converting carbon dioxide (CO 2 ) electroreduction into high value-added products is to obtain highly selective electrocatalysts. Research has shown that cuprous oxide (Cu 2 O) effectively facilitates the activation of CO 2 and suppress the competing hydrogen evolution reaction. However, during the process of electrochemical reduction, the valence state of Cu 2 O is prone to transformation. Herein, a series of Cu 2 O–CeO 2 -X catalysts (X represents different amounts of CeO 2 added) by applying Cu 2 O onto Cerium oxide (CeO 2 ) nanorods were synthesized via the impregnation method and used as electrocatalysts. We found that the Faradaic efficiency of methane (FE-CH 4 ) for Cu 2 O–CeO 2 -2 reached 65.1 % at −1.6 V vs. RHE, exceeding many catalysts previously reported. From the Cu LMM Auger spectra, it was found that the valence state of Cu species in Cu 2 O–CeO 2 -2 is mainly Cu 0 (accounting for 93.39 %), while in Cu 2 O–CeO 2 -3, the proportion of Cu 0 is 56.34 %. This indicates that CeO 2 has a regulatory effect on the valence state of Cu species. Additionally, we observed the valence state of Cu in Cu 2 O–CeO 2 -2 after the CO 2 reduction reaction and found that the proportion of Cu 0 changed little (94.97 %), which proves that CeO 2 plays a role in stabilizing the valence state of Cu. Research has demonstrated that Cu 0 can adsorb the ∗CO intermediate on its surface, followed by a hydrogenation reaction to generate CH 4 (∗CO + H + + e − → ∗CHO). Copper-based catalysts in which Cu 0 dominates among the Cu species are conducive to the conversion of CO 2 into CH 4 . In situ ATR-SEIRAS spectra confirmed the presence of key intermediates such as ∗CHO and explored the formation pathway of CH 4 (CO 2 → ∗COOH → ∗CO → ∗CHO → ∗OCH 2 → CH 4 ). This study provides a new way to design efficient copper oxide-based catalysts for CO 2 electroreduction by adjusting and stabilizing the ratio of copper valence state reasonably.
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
POLYHEDRON
·
2025
·
IF 2.6
Jia-Peng Cao,Qianxiang Xu,Yuanhang Ren,Hehua Hui,Jining Shang,Bin Yue,Heyong He
Three Cu-based polyoxomolybdate coordination polymers, [Cu I x Cu II 1-x (mbpy)(H 2 O)][Cu II (mbpy)(H 2 O) 2 ][Na(HPO 4 )(H x PO 4 )-Mo 5 O 15 ]·5·.5H 2 O ( 1 ), Cu(mbpy)Mo 2 O 7 ( 2 ) and [(Cu II (mbpy))(Cu I y Cu II 1-y (mbpy))(H 2 O)(H y PO 4 )] 2 [H 3 PMo VI 10 Mo V 2 O 40 ]·H 2 O ( 3 ) (mbpy = 4,4′-dimethyl-2,2′-dipyridyl, 0 < x < 1, 0 < y < 1), have been hydrothermally synthesized. Single crystal X-ray diffraction analysis of compounds 1 – 3 indicates that three different types of polyoxomolybdate unit, namely Strandberg-type {P 2 Mo 5 }, dimeric {Mo 2 } and Keggin-type {PMo 12 }, are included, respectively. Compound 1 is constructed by Strandberg-type {P 2 Mo 5 } and Cu(mbpy) to form a dimeric unit. Compound 2 has a 1D nanorod-like structure connected by the simplest {Mo 2 } unit. Compound 3 is an isolated structure consisting of a Keggin-type {PMo 12 } and a {Cu 4 } unit. BVS and XPS studies demonstrate that both Cu + and Cu 2+ coexist in compounds 1 and 3 , and magnetic measurement indicates the existence of anti-ferromagnetic interactions in compounds 1 – 3 . We proposed three possible magnetic modes, namely {Cu 4 }, linear {Cu 2 } and {Cu 4 -Mo 2 }, to explain the complex magnetic behavior and try to use both magnetic study and the structure analysis to probe the Cu(I) centers in the compounds.
研究领域:
材料化学
·
磁性材料
✓ 已验证
DOI
高影响因子
Catalysts
·
2025
·Vol. 15
·期 3
·277
·
IF 4
Yunhan Pu,Huajie Zhang,Yanjun Li,Chuan Yu,Xiaofei Song,Chen Yang,Mingli Fu
The conversion of methane (CH4) to methanol (CH3OH) under mild conditions remains a significant challenge in catalysis. In this study, we introduce a method to adjust the surface valence states of copper species in Cu-ZSM-5 catalysts by annealing under different atmospheres (N2, air, and H2). Among these, the 10% Cu-ZSM-5 catalyst calcined in H2showed outstanding performance, achieving a methanol productivity of 8.08 mmol/(gcat·h) and 91% selectivity at 70 °C and 3 MPa using H2O2as the oxidant. Comprehensive characterization revealed that H2annealing optimized the Cu surface to a lower valence state (predominantly Cu+), enhancing CH4adsorption and promoting H2O2activation to generate ·OH and ·CH3radicals, which drive selective CH3OH formation. In situ DRIFTS and radical trapping experiments further confirmed the critical role of Cu+in facilitating C-H bond cleavage and suppressing overoxidation.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nanomaterials
·
2024
·Vol. 14
·期 23
·1930
·
IF 4.4
Sha Ni,Wenjing Wu,Zichao Yang,Min Zhang,Jianjun Yang
The Cu cocatalyst supported on the surface of TiO2photocatalysts has demonstrated unique activity and selectivity in photocatalytic CO2reduction. The valence state of copper significantly influences the catalytic process; however, due to the inherent instability of copper’s valence states, the precise role of different valence states in CO2reduction remains inadequately understood. In this study, CuOx/TiO2catalysts were synthesized using an in situ growth reduction method, and we investigated the impact of various valence copper species on CO2photocatalytic reduction. Our results indicate that Cu+and Cu0serve as primary active sites, with the selectivity for CH4and CO products during CO2photoreduction being closely related to their respective ratios on the catalyst surface. The adsorption and activation mechanisms of CO on both Cu+and Cu0surfaces are identified as critical factors determining product selectivity in photocatalytic processes. Furthermore, it is confirmed that Cu+primarily facilitates CH4production while Cu0is responsible for generating CO. This study provides valuable insights into developing highly selective photocatalysts.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry C
·
2021
·Vol. 10
·期 2
·665-671
·
IF 7.393
Dandan Gao,Jiyang Xie,Jian Wang,Wanbiao Hu
It is widely accepted that localized electron hopping induces colossal permittivity in the bulk of transition-metal-based materials. However, the mechanism and the control of the electron hopping process remain to be explored. In this work, the effect of the B-site environment and multiple Cu valence-states on electron hopping were experimentally revealed in the LiCuNb2.95M0.05O9 (M = Mg, Ti) systems. The results demonstrated that Mg/Ti substitution for Nb5+ at the B-site effectively causes multivalent states of A-site Cu cations, i.e. Cu+/Cu2+/Cu3+, and distorted NbO6 octahedra. Upon Mg/Ti substitution, the dielectric permittivity was enhanced by approximately two orders of magnitude (at 1 kHz and 300 K) and an additional dielectric relaxation was induced. More importantly, it was revealed that the B-site substitution effectively adjusted the activation energy and average distances for the electron hopping.
研究领域:
材料科学
·
凝聚态物理
✓ 已验证
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Dongmin Zhao,Zhe Hong,Jiantao Liu,Lingling Yin,Hui Bai,Xiaodong Wang,Zhihua Gao,Wei Huang
The valence state and size of copper species play a critical role in the conversion of syngas to higher alcohols. In this study, CuAl binary catalysts with tunable Cu + -Cu 0 ratios and broad size distributions were successfully synthesized by adjusting the heat-treatment pressure of complete liquid-phase method, and their performance in CO hydrogenation was evaluated. The characterization results demonstrated that increasing heat-treatment pressure led to a general increase in both the Cu species size and the Cu⁺/(Cu⁺+Cu 0 ) ratio. Additionally, heat-treated under high pressure significantly enhanced the interaction between the Cu and Al components, promoted the formation of oxygen vacancies on AlOOH, and facilitated electron transfer. Notably, the oxygen vacancy content exhibited a linear correlation with the Cu + /(Cu + +Cu 0 ) ratio. The catalytic performance revealed a synergistic effect between the valence state and size of copper species in promoting higher alcohol synthesis. The percentage of C 2+ OH increased with the rise in Cu + /(Cu + +Cu 0 ) ratio and the size of Cu 0 and Cu 2 O. Among the catalysts, C-4 exhibited the largest Cu 0 and Cu 2 O sizes and the highest Cu⁺/(Cu⁺+Cu 0 ) ratio, achieving the highest proportion of higher alcohols (53.52 %). In-situ DRIFTS experiments also confirmed the synergistic effect of both factors. Larger Cu particles facilitated the dissociative adsorption of CO, while Cu⁺ sites favored the non-dissociative adsorption of CO. This work significantly expands the understanding of the role of Cu + -Cu 0 ratios and larger copper species in syngas conversion, offering valuable insights for the design of Cu-based catalysts with a high selectivity toward C 2+ OH.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2025
·
IF 15.7
Ren Yuqi,Cheng Miao,He Hongbin,You Changjun,Duan Lunbo,Sun Zhenkun,Peng Ruoxuan,Zhu Yuan-Hao,Zhang Hongyang,Zhou Jiancheng,Huang Kai,Guan Jie,Li Naixu
CO 2 -to-hydrocarbon fuel conversion via artificial photosynthesis is limited by catalyst poisoning under high O 2 partial pressures and sluggish C 2 -product formation. Herein, Ru 0.6 Cu 1 (Cu 0 –Cu 1+ )/CeO 2 catalysts with adaptive O 2 tolerance are prepared by O 2 -mediated dynamic interfacial reconstruction. Single-atom Ru doping at Ce lattice sites creates a trigonal prismatic coordination configuration, enabling proton-coupled electron transfer and accelerating H 2 O dissociation. Photothermal effect promotes O 2 -driven self-assembly of Cu 0 –Cu 1+ charge-gradient interfaces within Ru/Cu alloy clusters, thereby optimizing the adsorption behavior of * CHOCO intermediates and restructuring the C–C coupling pathway. Interfacial charge cascade transfer and geometric site synergy thermodynamically shift the product selectivity from C 1 to C 2 , as determined by operando spectroscopy and electronic structure analysis. Under concentrated solar irradiation, the catalyst produces 549 ± 20 μmol·g −1 C 2 H 4 with 74.3% selectivity and 0.5% solar-to-chemical energy conversion efficiency—25-fold higher than that in non-concentrated systems. Dynamic interfacial regulation facilitates precise carbon chain synthesis in complex reaction networks.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Yuxi Wang,Qizhao Zhang,Botao Fan,Qinghu Tang,Feng Qiu,Qiu-E Cao,Wenhao Fang
Photocatalysis could pave a way to converting biomass resources to high-valued chemicals and fuels under very mild conditions. However, the most popular and active TiO 2 photocatalyst is still encountered with selectivity-controlling troubles because of the complex reactivity between diverse reactants and radicals. In addition, TiO 2 -based catalysts are rarely explored in photoreduction of biomass derivatives. Here, this work reports heterojunction construction of Cu/TiO 2 , Cu 2 O/TiO 2 and CuO/TiO 2 photocatalysts for reductive transformations of bio-aldehydes to the corresponding α,β-unsaturated alcohols under simulated sunlight. CuO/TiO 2 achieves 100% furfural conversion with 96% furfuryl alcohol selectivity and 502 mg FOL g cat. −1 h −1 productivity, outperforming almost all copper- and titanium-oxide based catalysts in the literature to date. Incorporating copper to TiO 2 enables enhanced chemisorption of the C=O bond in furfural on catalyst surface, and moreover, increasing copper valence state can accelerate separation efficiency of photogenerated charge carriers. As a result, furfuryl alcohol selectivity as well as furfural initial conversion rate is significantly boosted. Photoelectrochemical measurements, in situ EPR and DRIFT-IR techniques, and DFT calculations coherently demonstrate photogenerated electrons and holes to be the critical active species driving the selective photoreduction process. Specifically, holes could promote proton reduction via methanol oxidation to generate highly reactive hydrogen species, while electrons would directly participate in the electron transfer process to selectively reduce furfural. To the best of our knowledge, this work can be the first example of success in controlling product selectivity using heterojunction strategy for photocatalytic reductive transformation of biomass derivatives and in achievement of high productivity for α,β-unsaturated alcohols.
研究领域:
光催化
·
材料科学
·
催化
·
绿色化学
·
生物质转化
✓ 已验证
产品关联
DOI
高影响因子
Journal of Water Process Engineering
·
2025
·
IF 6.7
Yuetong Wan,Ziqing Yan,Haojun Pan,Xiaodan Zhao,Zhongmin Fang
Peracetic acid based advanced oxidation processes have been widely applied in the treatment of antibiotics in the aquatic environments, in which the efficacy is constrained by the limited >Cu(II)/>Cu(I) redox cycling. Herein, the copper oxide loaded on straw-derived biochar (CuO@BC) is designed based on the superior electron transfer ability of biochar, which can significantly enhance the redox transformation from >Cu(II) to >Cu(I). The copper species in CuO@BC exists as monoclinic CuO crystals, and the biochar is rich in oxygen- and nitrogen-containing functional groups. The CuO@BC/PAA system can achieve TC removal rate of 98 % within 30 min of reaction. Within the pH range typical of real wastewater (pH = 5–9), this system maintains a high TC removal efficiency (>95 %), demonstrating excellent TC degradation performance. According to the radical quenching experiments, EPR analysis and product ion spectra, acetylperoxy radical and hydroxyl radical play key roles in TC degradation. >Cu(II) in CuO@BC acts as an active site to activate PAA, in which the redox cycle between >Cu(II) and >Cu(I) enhanced by the biochar continuously reacts with PAA. The abundant ketonic carbonyl and graphitic/pyrrole nitrogen in CuO@BC also serve as active sites, contributing significantly to the generation of singlet oxygen via a non-radical pathway for TC degradation. The CuO@BC/PAA system is applicable to various real water matrices. This study demonstrates efficient TC degradation based on the electron transfer capacity of biochar and copper valence cycling, highlighting the promising application potential of the system.
研究领域:
环境科学
·
水处理技术
·
高级氧化过程
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污染物降解
·
环境功能材料
✓ 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）