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.
研究领域:
电化学
·
催化材料科学
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DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2023
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IF 7.2
Xiuting Wu,Zefeng Zheng,Liang Ma,Changsong Hu,Yunhong Pi,Tiejun Wang
The aqueous-phase reforming of methanol(APRM)via non-precious metal heterogeneous catalysts is highly desirable, but challenging. Herein, we report a highly efficient copper catalyst encapsulated by chitosan-glucose (CS-G) conjugate with high metal loading of 35 wt% for H 2 generation from APRM. The optimized Cu@CS 19 -G 1 -300 catalyst exhibited exceptional activity of 1.39 × 10 5 μmol H2 /g cat /h at low temperature of 210 °C, which was ∼4.5 times higher than that of commercial CuZrAl catalysts (2.88 × 10 4 μmol H2 g cat −1 h −1 ). The chitosan-glucose conjugate acted not only as the main carbon support for Cu dispersion, but also as adsorbent to stablize as many Cu ions as possible. And meanwhile, with abundant Cu + /Cu 0 interface sites due to the reducing effect of glucose, the water gas shift reaction (WGSR) was intensified and thus displayed excellent selectivity toward CO by-product. This specific catalyst construction for H 2 production from APRM exhibits great potential of on-site H 2 supply for polymer membrane fuel cells.
研究领域:
化学工程
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催化科学
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能源材料
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DOI
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Long Cheng,Rong Wang,Wenzhe Si,Yanxi Deng,Junhua Li,Yue Peng
Cu-based catalysts leveraging Cu+/Cu0 active sites have emerged as pivotal for synthesizing essential hydrocarbons and alcohols in electrochemical CO2 reduction, such as ethylene and ethanol (C2 products). However, the dynamic reduction of Cu+ to Cu0 during electroreduction leads to site instability, resulting in diminished efficiency for CO2 conversion to C2 products. Herein, we introduced Si into CuO by the selective dissolution method, engendering Cu–O–Si units to stabilize the Cu+/Cu0 sites. The catalyst manifested good activity in CO2 electroreduction with an elevated Faradaic efficiency for C2 products reaching 81.9% at −100 mA/cm2. After ten cycles of electrochemical testing, the Cu+/Cu0 sites and performance exhibited no signs of degradation. The Si incorporation significantly improved the hybridization of O 2p and Cu 3d orbitals, thereby reinforcing the Cu–O bonds and stabilizing the Cu+/Cu0 sites, which was critical in promoting C–C coupling via decreasing the energy barriers for *OCCO formation and enhancing C2 product selection. The active Cu+ cations with unsaturated coordination contributed to the reaction stabilization, thereby improving the preservation of Cu2O metastable state.
研究领域:
电化学
·
催化
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材料科学
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能源转化
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DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 4
·673
·
IF 3.9
Jinghu Zhu,Hui Liu,Xueyan Zhou,Zhijun Wang,Liancheng Bing,Dezhi Han,Guangjian Wang,Fang Wang
Cu-based catalysts, modified by gallium addition via the stepwise co-precipitation method, were studied for the liquid phase hydrogenation of hydroxypivalaldehyde (HPA) to neopentyl glycol (NPG). Through physico-chemical techniques, the effects of gallium introduction on the Cu trimetallic catalyst performance and the reaction mechanism of HPA hydrogenation were discussed. The characterization results showed that gallium introduction can influence the dispersion, reduction, and distribution of active Cu species, as well as their reactivity. Herein, the catalyst with 2 wt% gallium addition exhibited excellent catalytic performance with HPA conversion rate and NPG selectivity of 93.5% and 95.5%, at a reaction pressure of 3 MPa, temperature of 110 °C, hydrogen-aldehyde ratio (molar ratio) 10:1, and liquid space-time at a speed of 8.4 h−1. The good performance could be attributed to gallium doping tending to dynamically tune the interaction between the components, increasing Cu dispersion and the distributions of Cu+and Cu0species on the catalyst surfaces.Keywords:HPA hydrogenation;NPG synthesis;Cu-based catalyst;gallium modification;Cu+/Cu0
研究领域:
化学工程
·
催化材料
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产品关联
DOI
高影响因子
Arabian Journal of Chemistry
·
2022
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IF 6.212
Lusheng Shi,Pengquan Yan,Zhihua Gao,Wei Huang
Due to the complexity of the structure–activity relationship of the CuAl 2 O 4 spinel catalyst, optimization of the catalyst structure is a great challenge. In this paper, three different CuAl 2 O 4 spinel catalysts were prepared by the solid-phase method using copper hydroxide, copper nitrate, and copper oxide as the copper source, respectively, to study the difference in the structure of CuAl 2 O 4 spinel catalysts induced by the raw materials and the catalytic behavior for CO hydrogenation. The structure of CuAl 2 O 4 spinel catalyst was characterized by XRD, BET, SEM, TEM, H 2 -TPR and XPS. The activity of CO hydrogenation over the CuAl 2 O 4 spinel catalyst without pre-reduction was evaluated in the slurry reactor. The results demonstrated that different copper sources had obvious influence on the CuAl 2 O 4 spinel texture properties, surface enrichment degree, as well as decomposition and reduction ability, which further regulated the ratio of Cu + /Cu 0 and thus affected the catalytic performance, especially the alcohol distribution. The CuAl 2 O 4 spinel, employing copper hydroxide as the copper source, showed better selectivity of C 2+ OH, which was assigned to a higher ratio of Cu + /Cu 0 , along with larger pore size and pore volume. Moreover, the synergistic effect between Cu 0 and γ-Al 2 O 3 improved the selectivity of dimethyl ether.
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
Molecular Catalysis
·
2024
·
IF 3.9
Nan Xi,Shiting Chen,Ruixi Bao,Qinglian Wang,Yixiong Lin,Jun Yue,Rong Wang,Chen Yang,Wang Yin,Ting Qiu
Furfuryl alcohol (FOL) is commercially available by selective hydrogenation of furfural (FAL). A variety of catalysts have been developed for such purpose, among which Cu-based catalysts show superior catalytic performance. However, copper nanoparticles with complex valence states are easy to agglomerate during hydrogenation reaction, which might have a negative influence on the catalytic performance. The carbon coating is an efficient strategy to prevent the sintering of Cu-based catalysts. Herein, a strategy based on the thermal decomposition of Cu-EDTA complex was designed to prepare carbon encapsulated Cu-based catalysts. The prepared catalysts were applied in the selective hydrogenation of FAL to FOL in the batch reactor. The results showed that a nearly quantitative conversion of FAL with a selectivity of 98.7 % towards FOL was achieved using CuO x @NC-150 (molar ratio of Cu: Na 4 EDTA·4H 2 O=2:1; obtained by oxidative activation at 150 °C) under 140 °C, 3 MPa in 4 h. The performance was comparable to that of the commercial CuCr 2 O 4 catalyst under the identical conditions. In addition, the developed carbon encapsulated Cu-based catalysts exhibited a slightly better stability than CuCr 2 O 4 catalyst in terms of FOL yield in five consecutive cycles. XPS and XAES characterizations implied that the presence of a suitable surface ratio of Cu + /(Cu + +Cu 0 ) of the prepared catalyst may contribute to the selective hydrogenation of FAL to FOL.
研究领域:
催化化学
·
绿色化学
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DOI
高影响因子
ChemSusChem
·
2026
·Vol. 19
·期 1
·e202501680
·
IF 6.6
Jinlong Wu,Haiqiang Mu,Min Zhu,Xueru Zhao,Ting Zhang,Jiaxin Bai,Jin Zhang,Feng Li,Jing Li
Copper-based catalysts offer promise for CO 2 -to-C 2+ conversion but suffer from instability of Cu + species, which are active sites critical for enabling C−C coupling. In this work, we synthesized Lanthanum (La)-doped Cu x O (La-Cu x O) catalysts with varying La/Cu ratios to investigate how the interplay between doping-induced electronic effects and grain boundary (GB)-driven stabilization affects deep CO 2 reduction to C 2+ . Combined density functional theory calculations and in situ spectroscopic characterization reveal that the unique 4f orbital configuration and strong Lewis acidity facilitate charge transfer of La, stabilizing Cu + during CO 2 reduction reaction (CO 2 RR), while simultaneously inducing lattice distortion to increase GB density. This modulation preserves Cu + /Cu 0 interfaces while enhancing *CO dimerization kinetics. Furthermore, La doping boosts *CO coverage at GB-rich regions and lowers the C−C coupling barrier. The optimized La-Cu x O-2 catalyst (La/Cu = 0.224) achieves a 45.2% C 2 H 4 Faradaic efficiency (FE) and 75.4% C 2+ FE at −0.8 V RHE , with partial current densities of 87.5 and 146.7 mA cm −2 , respectively, surpassing undoped Cu x O. Remarkably, it retains more than 90% initial activity after 24 h operation, demonstrating exceptional stability. This work provides a rational strategy for stabilizing Cu + and tailoring pathways via rare-earth doping. Graphical La doping stabilizes Cu + /Cu 0 interfaces via electronic modulation and lattice distortion, enhancing grain boundary density in Cu x O catalysts for efficient CO 2 electroreduction. The optimized La-Cu x O-2 achieves 75.4% C 2+ Faradaic efficiency and 146.7 mA cm −2 partial current density at −0.8 V versus reversible hydrogen electrode, suppressing hydrogen evolution and enabling scalable CO 2 -to-C 2+ conversion.
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DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2026
·
IF 7.6
Jiahui Zhou,Ziyi Zhang,Chenghao Jin,ShanShan Tong,Yunteng Qu
Electrochemical CO2 reduction reaction (CO2RR) to diverse high-value chemicals represents a promising carbon mitigation strategy, yet precisely controlling product selectivity remains a considerable challenge. Herein, we report a size-dependent Cu/CN catalyst for modulating the selectivity of CO2RR. Specifically, small Cu NPs on CN (∼5 nm, S–Cu/CN) achieved a 76.2% C2+ product selectivity at 0.6 A cm–2, while the large one (∼50 nm, L-Cu/CN) reached a 67.5% CH4 selectivity at 0.6 A cm–2. Physical characterizations revealed that S–Cu/CN displays partial Cu+ sites, whereas L-Cu/CN higher Cu+ content. Mechanism analysis revealed a balanced Cu0/Cu+ ratio in S–Cu/CN promotes C–C coupling at Cu+ sites to form C2+ products. Conversely, higher Cu+ content in L-Cu/CN decreased the *CO coverage and improved H2O dissociation, steering continuous hydrogenation toward CH4 generation. This work offers a novel strategy to design high-efficiency CO2RR electrocatalysts toward desired products.
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Kai Zhu,Zihan Lin,Xinyi Bai,Fangfang Chang,Qing Zhang,Xiaolei Wang,Zhengyu Bai
Electrocatalytic reduction reaction of CO2 (CO2RR) into value-added multicarbon (C2+) products represents a sustainable strategy for mitigating greenhouse gas emissions and enhancing the production of high-value chemicals. Cu-based catalysts are optimal for the CO2RR, facilitating the generation of C2+ products such as ethanol, which have significant industrial applications. However, converting CO2 to C2+ products remains a great challenge, necessitating the simultaneous achievement of high current density, Faradaic efficiency (FE), and operational stability for industrial-scale implementation. Herein, we prepared Cu/Cu2O catalysts with diverse morphologies and the ratio of the Cu+/Cu interface, which was rectified by regulating the interactions between the active interface and the intermediate (*CO). The electrochemical analysis demonstrated that reconstructed Cu/Cu2O nanodendrites with dominant grain boundaries exhibited remarkable performance in generating C2+ products, achieving a Faradaic efficiency (FE) of 71.8%, including 49.7% FE of ethanol and a substantial partial current density of 390.0 mA cm–2 within the flow cell. In situ spectroscopy characterization and theoretical calculations revealed that the increased ethanol selectivity originated from the rectification of the Cu/Cu2O interface by the *CO intermediate, which accelerated H2O dissociation, reduced the free energy for *CO hydrogenation to *COH, and facilitated asymmetric *CO-*COH coupling to preferentially reduce CO2 to ethanol. This study provides profound insights into the C–C coupling pathways and sheds light on the rational design of ethanol-oriented electrocatalysts, contributing to sustainable chemical synthesis and energy utilization.
研究领域:
电催化
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能量转换
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材料科学
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环境化学
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化学工程
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
·
IF 9.7
Man Zhao,Wei Wen,Chunmei Liu,Qinyun Yan,Shuai He,He Xiao,Li Zhang,Junming Zhang,Xiaofeng Gao,Jianfeng Jia
The electrochemical CO 2 reduction reaction (CO 2 RR) to multi‑carbon products offers a promising route for sustainable fuel production, yet achieving high selectivity remains challenging due to the complex interplay between catalyst structure and reaction pathways. Here, we report a rational design of Cu-Cu 2 O/graphene (Cu/G) composites with tunable Cu + /Cu 0 ratios via electrolyte-mediated electrochemical synthesis. By varying tetraalkylammonium/phosphonium electrolytes (TBABF 4 , TBAPF 6 , TBACF 3 SO 3 , TBPBF 4 ), we precisely control Cu oxidation states, as validated by the results of X-ray absorption fine structure (XAFS), X-ray diffraction (XRD), and high-resolution transmission electron microscope (HRTEM). In-situ Fourier transform infrared (In-situ FTIR) spectra and in-situ Raman spectra indicate Cu + -rich surfaces (Cu/G-TBABF 4 ) favor the production of formate via O-bound intermediates, while Cu 0 -dominated interfaces (Cu/G-TBAPF 6 ) promote the formation of CO through C-bound pathways. Mixed Cu + /Cu 0 systems (Cu/G-TBACF 3 SO 3 , Cu/G-TBPBF 4 ) enable C C coupling, with ethylene (FE = 28 %) and ethanol (FE = 30.2 %) selectivity governed by the Cu + /Cu 0 balance. Ultraviolet photoelectron spectroscopy (UPS) results reveal that lower work functions enhance *CO coverage and stabilize C 2+ intermediates, elucidating the electronic structure-activity relationship. This work demonstrates electrolyte-mediated oxidation state engineering as a versatile strategy to steer CO 2 RR pathways, offering a generalizable approach for designing multi-valent electrocatalysts with tailored selectivity.
研究领域:
电催化
·
材料科学
·
能量转换
·
表面化学
·
光谱学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nano Energy
·
2023
·
IF 17.6
Hao Zhang,Ying Wang.,Qiong Lei,Ying Wang,Chiu Tang,Jun Yin,Tsz Woon Benedict Lo
Tracking the evolution of electrocatalysts over oxide-derived Cu materials during the electrochemical CO 2 reduction reaction (eCO 2 RR) is pivotal for optimizing the product selectivity toward desired multi-carbon (C 2+ ) products. However, the identification of the true intermediate active catalyst is still unclear. Here, we adopted a multi-modal characterization approach, primarily based on operando powder X-ray diffraction and operando micro-Raman spectroscopy, to study three Cu 2 O precursors with different morphologies, namely, octahedral (O-), cubic (C-), and nanowire (N-Cu 2 O). This multi-modal approach allows us to investigate the Cu 2 O nano-crystallites from the interface to the bulk structure. The results suggested notably different electrochemical reduction kinetics. 26.1% O-Cu 2 O and 90.6% C-Cu 2 O were reduced to much smaller Cu(0) domains after two hours of time-on-stream; N-Cu 2 O, with notably higher surface-to-volume ratio, was completely reduced within 45 min of time-on-stream. We accordingly observed a structure-reactivity correlation where a more intricate Cu 2 O/Cu grain network (and hence Cu + -Cu 0 junctions) as observed in O-Cu 2 O, can lead to stable and quantitative production of ethylene at the Faradic efficiency of around 40% (in stark contrast to those of C- and N-Cu 2 O). The synergy between the Cu 2 O and Cu phases was also verified by density functional theory calculations. The upshifted d -band center of Cu 2 O/Cu in O-Cu 2 O is the most conducive toward the production of ethylene, whereas the downshifted d -band center of Cu 2 O/Cu in C-Cu 2 O leads to a decreased production of ethylene in the expense of unwanted production of hydrogen. We envisage that system optimization and design of new catalysts will become more facile and efficient using a related multi-modal operando characterization philosophy.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Xiaoxiao Zheng,Jiaming Wang,Peipei Lei,Qihong Xue,Xian Kan,Jiangang Chen
An enhanced Cu + /Cu 0 catalytic structure via the electronic effect of K was fabricated; • The proper amount of K could regulate the ratio of Cu + /Cu 0 and promote Cu dispersion; • Both the enhanced Cu + /Cu 0 ratio and the smaller Cu size promote the generation of MG; • The increased basic sites by the K doping remarkably increase the ethers by-products; • The deactivation was caused by the boosted Cu + ratio and the coated active sites by K. In this work, the CuZr 2 catalysts with significantly enhanced Cu + /Cu 0 catalytic active structures via the electronic effect of K were synthesized by the means of citrate complexation and used for dimethyl oxalate (DMO) hydrogenation to methyl glycolate (MG). The CuZr 2 –1.0 K sample exhibited the most outstanding performance, achieving a DMO conversion of 93.4% and MG selectivity of 85.8%. And the role of K in Cu-based catalysts for DMO hydrogenation is universal. The reduction of the catalyst was inhibited after potassium addition, lowering the Cu 0 content, thus leading to a decrease in the H 2 adsorption capacity of the catalyst, and accordingly, its activity decreased. The results showed that the ratio of Cu + /Cu 0 increased after K doping, and the adsorption strength of the catalyst for H 2 was weakened, which inhibited the deep hydrogenation of DMO. Simultaneously, the smaller size of metallic Cu via the appropriate amount of K doping facilitated the desorption of MG. Therefore, the selectivity for the target product MG was remarkably improved. However, the basic sites on the catalyst surface could increase after K doping, which would lead to an increase in the ether by-products. As the reaction proceeded, the ability of the catalyst to adsorb and activate H 2 was diminished due to the significantly increased surface K content and Cu + ratio, leading to the deactivation of the K-doped catalyst. This study provides a potential pathway for alkali metals to regulate the electronic structure of Cu-based catalysts and apply them to the hydrogenation of DMO to MG. Download: Download high-res image (258KB) Download: Download full-size image
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高影响因子
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