Chem Catalysis
·
2024
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IF 11.5
Bihua Hu,Bingxian Chu,Hailin Cao,Zhiwei Lei,Shuyu Cui,Peizhi Wang,Jun Tang,Xingzhu Wang,Baomin Xu
Molecular catalysts with precisely designed structures and abundant metal-nitrogen active sites have garnered significant attention for their ability to efficiently perform electroreduction of carbon dioxide (ERCD). However, the catalytic efficiency and selectivity are significantly limited by the fixed electronic structure of the metal-nitrogen structure, resulting in low production efficiency of more valuable products. This work presents the electronic regulation of cobalt phthalocyanine (CoPc) through in situ oxidation of N-doped Ti 3 C 2 T x nanosheets (CoPc/o–N–MXene). The resulting material exhibits high activity and tailorable selectivity. The study confirmed a strong interaction between Co-N 4 active sites and N–MXene after oxidation, resulting in a “Co–N–MXene” bond. This bond contributes to the transformation of intermediate ∗ CO into ∗ HCO, leading to a high selectivity of ERCD to methanol. This work provides a perspective on the mechanism of ERCD to methanol and an avenue for the synthesis of effective catalysts.
研究领域:
材料科学
·
催化化学
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产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Mengmeng Zhang,Xu Chen,Hui Xue,Zhijia Zhang,Yang Wang,Yifang Zhang,Yida Deng,Yong Jiang
As an effective strategy to turn waste into treasure, electrochemical CO 2 reduction reaction (eCO 2 RR) producing value-added chemicals such as HCOOH attracts unremitting interest. However, the practical applications are limited by poor activity and selectivity, the key is to develop economical-efficient catalysts. Herein, gradient-doped Sn on the CuO surface (Sn-CuO) was developed for eCO 2 RR in an H-cell. Typically, the main reaction pathway of *OCHO → HCOOH was obtained via in situ experiments and further verified by theoretical calculations. Furthermore, the lowest Δ G *OCHO and Δ G *OCHO − Δ G *H as well as the highest Δ G *COOH enlist Sn-CuO with sufficient proton to produce HCOOH while inhibiting CO and H 2 by-products. Finally, the synthesized Sn-CuO delivers a maximum partial current density (23.6 mA cm −2 ) at −1.3 V REH and Faradic efficiency (91.5 %) at −1.2 V RHE for HCOOH, indicating excellent activity and selectivity.
研究领域:
材料科学
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电化学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
TRANSACTIONS OF TIANJIN UNIVERSITY
·
2021
·Vol. 28
·期 1
·73-79
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IF 0
Tian Pengfei,Su Jianjun,Song Yun,Ye Ruquan,Zhu Minghui
Great attention has been paid to cofacial porphyrins due to their many unique advantages over their monomeric analogs. However, their synthesis is usually complicated. In this work, a facile impregnation method for preparing heterogenized, cofacially stacked porphyrins is proposed. An anionic porphyrin is introduced as an underlayer for immobilization of cationic cobalt porphyrin via electrostatic force. The metal center of the underlying molecule contributes to the electronic structure of the upper cationic cobalt porphyrin. Screening reveals the anionic iron porphyrin to be the most efficient underlayer molecule, lowering the activation energy barrier of CO 2 electroreduction, with an improved turnover frequency by 74% to 8.0 s −1 at − 0.6 V versus RHE.
研究领域:
化学
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材料科学
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催化
✓ 已验证
DOI
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
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IF 9.4
Fuming Liu,Mei Luo,Keliang Wang,Ziwei Li,Fei Liu,Min Li
Electrochemical CO 2 reduction reaction (CO 2 RR) is one of the most attractive measures to achieve the carbon neutral goal by converting CO 2 into high-value chemicals such as formate. Si in Bi silicates is promising to enhance CO 2 adsorption and activation due to its strong oxygenophilicity. Whereas, its role in boosting CO 2 RR via the cheap Bi-based catalysts is still not clear. Herein, we design CNT@Bi silicates catalyst, demonstrating the highest FE HCOOH of 96.3 % at −0.9 V vs . reversible hydrogen electrode with good stability. Through X-ray photoelectron spectroscopy (XPS), in-situ Attenuated Total Reflectance-Fourier Transform Infrared ( In-situ ATR-SEIRAS) experiments, and Density Functional Theory (DFT) calculations, the role of Si in Bi silicates was unveiled: tuning the electronic structure of Bi, weakening the Bi-O bond, and strengthening electron transfer from Bi to CO 2 , thereby promoting the generation of CO 2 * − and *OCHO intermediates. Additionally, carbon nanotubes (CNTs) promote not only the conductivity but also the generation of abundant oxygen vacancies in CNT@Bi silicates evidenced by the electron transfer from CNT to Bi silicates from XPS results. Further, the CNT@Bi silicates endows it with the highest electrochemical activation area. These findings suggest the effectiveness of Si in Bi silicates and structure tuning to design highly selective CO 2 RR catalyst for HCOOH production.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
ACS Nano
·
2021
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IF 15.881
Peilong Lu,Xin Tan,Haitao Zhao,Qian Xiang,Kaili Liu,Xiaoxu Zhao,Xinmao Yin,Xinzhe Li,Xiao Hai,Shibo Xi,Andrew T S Wee,Stephen J. Pennycook,Xuefeng Yu,Menglei Yuan,Jianbo Wu,Guangjin Zhang,Sean C. Smith,Zongyou Yin
An atomically dispersed structure is attractive for electrochemically converting carbon dioxide (CO2) to fuels and feedstock due to its unique properties and activity. Most single-atom electrocatalysts are reported to reduce CO2 to carbon monoxide (CO). Herein, we develop atomically dispersed indium (In) on a nitrogen-doped carbon skeleton (In–N–C) as an efficient catalyst to produce formic acid/formate in aqueous media, reaching a turnover frequency as high as 26771 h–1 at −0.99 V relative to a reversible hydrogen electrode (RHE). Electrochemical measurements show that trace amounts of In loaded on the carbon matrix significantly improve the electrocatalytic behavior for the CO2 reduction reaction, outperforming conventional metallic In catalysts. Further experiments and density functional theory (DFT) calculations reveal that the formation of intermediate *OCHO on isolated In sites plays a pivotal role in the efficiency of the CO2-to-formate process, which has a lower energy barrier than that on metallic In.
研究领域:
化学
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材料科学
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催化反应
✓ 已验证
DOI
高影响因子
iScience
·
2024
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IF 4.6
Qi Xu,Wentao Wang,Yangyang Zhang,Huanhuan Liu,Xiaowen Wang,Suyuan Zeng,Genqiang Zhang
The production of high-demand syngas with tunable ratios by CO 2 electroreduction has attracted considerable research interest. However, it is challenging to balance the evolution performance of H 2 and CO with wide H 2 /CO ratios, while maintaining high efficiency. Herein, nitrogen-coordinated hierarchical porous carbon spheres with varying phosphorus content (P x NC-T) are assembled to regulate syngas production performance. The precise introduction of P modulates the local charge distribution of nitrogen-coordinated carbons, thereby accelerating the protonation process of ∗ CO 2 -to- ∗ COOH and promoting moderate H ∗ adsorption. Specifically, syngas with wide H 2 /CO ratios (0.60–4.98) is obtained over a low potential range (−0.46 to −0.86 V vs. RHE). As a representative, P 1.0 NC-900 presents a remarkable current density (−152 mA cm −2 ) at −1.0 V vs. RHE in flow cells and delivers a decent peak power density (1.93 mW cm −2 ) in reversible Zn-CO 2 batteries. Our work provides valuable insights into the rational design of carbon-based catalysts for CO 2 reduction.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nature Synthesis
·
2024
·Vol. 3
·期 7
·891-902
·
IF 0
Cai Yanming,Yang Ruixin,Fu Jiaju,Li Zhe,Xie Liangyiqun,Li Kai,Chang Yu-Chung,Ding Shichao,Lyu Zhaoyuan,Zhang Jian-Rong,Zhu Jun-Jie,Lin Yuehe,Zhu Wenlei
The selective one-step CO 2 electroreduction reaction (CO 2 RR) to acetate and propanol has garnered intense interest. Here we report the design of self-pressurizing nanoscale capsule catalysts for the CO 2 RR. A high-pressure CO intermediate environment is created around copper catalysts by a permselective enclosure. Microkinetic modelling, 13 CO 2 / 12 CO co-feed experiments and in situ Raman spectroscopy confirm that a unique CO–CO 2 coupling path is involved, which is only initiated at high CO intermediate pressure. This pathway benefits acetate production due to the kinetic and energetic advantages of COCO 2 *. The acetate Faradaic efficiency is 38.5 ± 2.2% (8 times higher than that achieved without enclosure) and the acetate partial current density is 328 ± 19 mA cm −2 , which surpasses the performance of previous CO 2 RR catalysts. In situ investigation indicates that the CO pressure inside the nanoscale capsule catalysts can reach 8 ± 3 bar. Furthermore, self-pressurizing nanoscale capsule catalysts with a CuI-derived core can reduce CO 2 to propanol with a Faradaic efficiency of 25.7 ± 1.2% and a conversion rate of 155 ± 3 mA cm −2 .
研究领域:
材料科学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
ADVANCED FUNCTIONAL MATERIALS
·
2025
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IF 19
Lei Xiong,Xianbiao Fu,Jun Zhang,Shuang Liu,Shanshan Li,Shaojie Lu,Dong Wang,Qin Yue
Cu shows unique characteristics for electrochemical CO 2 reduction reaction (CO 2 RR) to hydrocarbons and oxygenates due to the moderate adsorption energy of the key intermediate *CO. However, it remains a challenge to selectively control CO 2 RR towards C 1 (e.g., CH 4 ) or C 2+ (e.g., C 2 H 4 and C 2 H 5 OH) through simple interface engineering. Herein, a series of inverse catalysts, composed of CeO 2 nanoparticles over Cu substrate (Cu-CeO 2 -x), are subtly designed to tackle the issues. It is verified CeO 2 decoration induces highly active Cu/CeO 2 interfacial sites that enhance the adsorption and conversion of CO 2 and *CO intermediates into C 2+ or CH 4 , while the Cu sites are conducive to *CO generation. With the increase of CeO 2 deposition, the C 2+ and CH 4 selectivity present a volcano-type and increasing tendency with maximum faradic efficiency of 62.6% and 51.3%, respectively. In-situ infrared spectroscopy and theoretical calculations reveal that moderate CeO 2 loading allows the Cu/CeO 2 interfacial sites to cooperate efficiently with the Cu sites to promote the coupling of *CO/*CHO intermediates, thus enhancing the C 2+ selectivity. In contrast, excessive CeO 2 loading suppresses the C─C coupling but boosts unilaterally the hydrogenation, thus promoting the CH 4 production. This work provides effective strategies to regulate the CO 2 RR selectivity by modulating metal/oxide interfaces.
研究领域:
材料科学
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电化学
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Xin Zong,Yingmin Jin,Xuebai Zhang,Jinqiu Zhang,Xue Li,Yueping Xiong
Electrochemical CO 2 reduction (ECR) is regarded as a potential approach to generate renewable fuel and realize carbon cycling. Zn-based materials have been considered as effective catalysts to reduce CO 2 into CO. Unfortunately, low selectivity for CO and Zn metallization impede the development of Zn-based materials. Herein, we propose a strategy in utilizing the changeable valence state of Ce ions to stabilize oxidation state of ZnO, in which the Zn-O-Ce model is constructed by CeO 2 -modified ZnO nanofibers through electrospinning technique. The effective stabilization of ZnO oxidation state during electroreduction has been verified via operando Raman spectra and other characterizations. Besides, we also find that the introduction of trace amount of inactive CeO 2 can not only suppress the hydrogen evolution reaction (HER), but also greatly enlarge active sites. The catalyst with optimized molar ratio of CeO 2 to ZnO exhibits high Faradaic efficiency (FE) of 90.00 % for CO at −0.69 V vs reversible hydrogen electrode (RHE) in a flow cell. This work suggests stabilization of oxidation state via introduction of secondary metal-oxide by strong interactions between atoms can be improved.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMOSPHERE
·
2021
·
IF 7.086
Da Wang,Shiwen Dong,Lingsha Wen,Weiting Yu,Zhiqiao He,Qingqing Guo,Xiaohui Lu,Lizhang Wang,Shuang Song,Jun Ma
A metal oxide electrode has been developed for the electrochemical CO 2 reduction reaction (eCO 2 RR). It exhibits superior activity and product selectivity towards eCO 2 RR by circumventing the previously encountered problem of self-reduction with high-valence metals. Specifically, a hydrocerussite [Pb 3 (CO 3 ) 2 (OH) 2 ] thin film has been synthesized in situ on a Pb substrate (denoted as ER-HC) by an electroreduction method using a lead-based metal–organic framework (Pb-MOF) as a precursor. The ER-HC electrode exhibits a high selectivity of 96.8% towards HCOOH production with a partial current density of 1.9 mA cm −2 at −0.88 V vs. the reversible hydrogen electrode (RHE). A higher HCOOH partial current density of 7.3 mA cm −2 has been achieved at −0.98 V vs. RHE. Physicochemical and electrochemical characterization results demonstrate that the defective hydrocerussite surface exhibits appropriate adsorption free energy of formate (HCOO − ) and a lower reaction free energy for HCOOH production from CO 2 , which greatly boosts the eCO 2 RR activity and HCOOH production selectivity. The structure and eCO 2 RR performance of the hydrocerussite thin film remain stable in 0.1 M KHCO 3 as electrolyte, ensuring its durability. Overall, this work not only provides a metal oxide electrode (metal hydroxide, to be more precise) with excellent eCO 2 RR performance, but also expands the in situ electrochemical derivatization strategy for the fabrication of metal oxide electrodes.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Bing Chang,Fengtao Zhang,Zhaojun Min,Nan Wang,Qingchun Xia,Jing Fan,Maohong Fan,Jianji Wang
Cu-based catalysts, especially co-sites of Cu 0 and Cu Ⅰ , are the best competitors for electrochemical CO 2 fixation to produce multi-carbon (C2 + ) products. However, it is challenging to construct highly stable Cu Ⅰ sites due to the changeability of its valence state and electronic structure in the electroreduction process, and the mechanism is also elusive. Herein, a 2D conductive Cu Ⅱ -MOF film (Cu Ⅱ HHTP@Cu 0 ) is prepared on Cu (1 0 0) foil by in-situ electrochemical assembly. After pre-reduction, the in-situ produced Cu 2 O clusters are confined in the cavities of the film created by the local breaking of the MOF framework to construct a unique Cu Ⅰ -Cu Ⅱ HHTP@Cu 0 catalyst, so that a novel strategy is proposed to stablize highly dispersed Cu Ⅰ sites during electrochemical reduction, thus protecting the Cu 2 O clusters from further reduction and ensuring the coexistence of Cu Ⅰ (1 1 1)-Cu 0 (1 0 0) sites. As such, the current density of CO 2 electrochemical reduction catalyzed by this catalyst exceeds 300 mA cm −2 , the duration overs 50 h, and the C2 selectivity achieves 72.6 %. In-situ spectroscopy and theoretical calculations reveal that the optimized microenvironment of the Cu Ⅰ (1 1 1) sites reduces the energy barrier of *OCCOH coupling, and Cu 0 (1 0 0) sites increase the coverage of *CO, thus boosting the production of C2 products.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Liang Fu,Zhenping Qu,Lingling Zhou,Yue Ding
Electrochemical CO2 reduction (ECR) to high value-added feedstocks is a sustainable way to address energy and environmental issues. However, there still exists a bottleneck in comprehending the structure–activity relationship of catalysts for ECR. Herein, we demonstrated that the simultaneous tuning of surface-adsorbed hydroxyl group (OHad) coverage and oxygen vacancy (OV) amount on the In2O3 surface was an effective approach to derive an excellent formate Faradaic efficiency (FE) of above 80% at a wide potential range from −1.0 to −1.5 V versus the reversible hydrogen electrode (vs RHE) with promising durability. Electrochemical experiments and theoretical analyses revealed that the synergistic effect of OHad and OV could smartly optimize the adsorption sites, accelerate the electron transfer, and stabilize *CO2•– and *OCHO intermediates, and thus facilitate ECR activity. This result will contribute to the understanding of the critical role of these surface oxygen species in ECR, which can offer valuable insights into the rational catalyst design for comprehensive utilization of CO2 with high energy efficiency.
研究领域:
化学
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材料科学
·
环境科学
✓ 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）