Nature Communications
·
2024
·Vol. 15
·期 1
·1-11
·
IF 14.7
Chen Fanpeng,Li Li,Cheng Chuanqi,Yu Yifu,Zhao Bo-Hang,Zhang Bin
Electrocatalytic semihydrogenation of acetylene (C 2 H 2 ) provides a facile and petroleum-independent strategy for ethylene (C 2 H 4 ) production. However, the reliance on the preseparation and concentration of raw coal-derived C 2 H 2 hinders its economic potential. Here, a concave surface is predicted to be beneficial for enriching C 2 H 2 and optimizing its mass transfer kinetics, thus leading to a high partial pressure of C 2 H 2 around active sites for the direct conversion of raw coal-derived C 2 H 2 . Then, a porous concave carbon-supported Cu nanoparticle (Cu-PCC) electrode is designed to enrich the C 2 H 2 gas around the Cu sites. As a result, the as-prepared electrode enables a 91.7% C 2 H 4 Faradaic efficiency and a 56.31% C 2 H 2 single-pass conversion under a simulated raw coal-derived C 2 H 2 atmosphere (~15%) at a partial current density of 0.42 A cm −2 , greatly outperforming its counterpart without concave surface supports. The strengthened intermolecular π conjugation caused by the increased C 2 H 2 coverage is revealed to result in the delocalization of π electrons in C 2 H 2 , consequently promoting C 2 H 2 activation, suppressing hydrogen evolution competition and enhancing C 2 H 4 selectivity.
研究领域:
化学工程
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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
ADVANCED FUNCTIONAL MATERIALS
·
2021
·Vol. 32
·期 5
·2106886
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IF 18.808
Haisheng Gong,Zengxi Wei,Zhichao Gong,Jingjing Liu,Gonglan Ye,Minmin Yan,Juncai Dong,Christopher Allen,Jianbin Liu,Kang Huang,Rui Liu,Guanchao He,Shuangliang Zhao,Huilong Fei
Electrochemical H 2 O 2 production through the 2-electron oxygen reduction reaction (ORR) is a promising alternative to the energy-intensive anthraquinone process. Herein, by simultaneously regulating the coordination number of the atomically dispersed cobalt sites and the nearby oxygen functional groups via a one-step microwave thermal shock, a highly selective and active Co N C electrocatalyst for H 2 O 2 electrosynthesis that exhibits a high H 2 O 2 selectivity (91.3%), outstanding mass activity (44.4 A g −1 at 0.65 V), and large kinetic current density (11.3 mA cm −2 at 0.65 V) in 0.1 m KOH is obtained. In strong contrast to the typical Co N 4 moieties for the 4-electron ORR, the present Co N C catalyst possesses a low-coordinated Co N 2 configuration and abundant epoxide groups, which work in synergy for promoting the 2-electron ORR, as demonstrated by a series of control experiments and theoretical simulations. This study may provide an effective avenue to modulating the composition and structure of electrocatalysts at the atomic scale, leading to the development of new electrocatalysts with unprecedented reactivity.
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
SEPARATION AND PURIFICATION TECHNOLOGY
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2022
·
IF 9.136
Shaolong Wang,Hao Liu,Dingding Ye,Qiao Lan,Xun Zhu,Yang Yang,Rong Chen,Qiang Liao
Both sustainable storage of renewable energy using H 2 O 2 as energy carrier and wastewater treatment by electro-Fenton are highly dependent on the efficiency of H 2 O 2 electrosynthesis via 2-electron reduction of O 2 . Rational design of high-performance and cost-effective electrocatalysts with facile preparation is bear the brunt of scalable H 2 O 2 electrosynthesis. Herein, for the first time, we synthesize a pitaya peel-derived formicary-like electrocatalyst employing facile pyrolysis and KOH activation. At the optimal mass ratio of biochar to KOH (1:3), the electrocatalyst exhibits prominent H 2 O 2 activity and selectivity owing to its rich self-doped oxygen-containing functional groups as well as structural defects and sp 3 -C bonds serving as reactive sites, rational hierarchical pores boosting mass transfer of reactants and products, and ultrahigh specific surface area facilitating the exposure of reactive sites. Under natural air diffusion, the pitaya peel-derived catalyst-coated cathode achieves surprising H 2 O 2 productivity of 41.6 mg h −1 cm −2 with current efficiency of 65.5% at large current density of 100 mA cm −2 , meeting the near-industrial requirements for sustainable H 2 O 2 production. Long-term operation stability at large current and rapid degradation of multiple high-concentration organic pollutants demonstrate tremendous potential of the pitaya peel-derived catalysts for H 2 O 2 -based renewable energy storage and environmental remediation.
研究领域:
材料科学
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环境科学
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能源科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE CHEMICAL LETTERS
·
2025
·
IF 8.9
Min Zhang,Weimin Wang,Jun Li,Xun Zhu,Qian Fu
Developing advanced electrocatalysts to convert CO 2 into liquid fuels such as C 2 H 5 OH is critical for utilizing intermittent renewable energy. The formation of C 2 H 5 OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu₂O nanowire array (OTT-Cu₂O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C 2 H 5 OH electrosynthesis via CO 2 RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO 2 -to-C 2 H 5 OH conversion at 300 mA/cm 2 , representing a more than two-fold enhancement over the Cu 2 O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH 2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH 2 , forming the critical CO–OCH₂ intermediate and facilitating C 2 H 5 OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO₂ reduction to C 2 H 5 OH and provides fundamental insight into the reaction mechanism.
研究领域:
电催化
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能源化学
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材料化学
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环境科学
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可持续能源
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表面科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Binxin Lv,Jiayue Yu,Fengchen Zhou,Zizi Wang,Junjun Zhang,Yifan Zhang,Yang Wu,Yong Wang,Wen Luo
Urea electrosynthesis plays a vital role in the nitrogen cycle, promoting carbon neutrality while also being energy-efficient. However, the complexities involved in the simultaneous of carbon and nitrogen-containing species significantly hinder the selectivity and yield of urea. In this study, we report a CuZn bimetallic catalyst that is capable of converting CO 2 and NO 3 ⁻ into urea, with a maximum Faraday efficiency of 40% at -0.6 V vs. RHE, alongside an impressive urea yield rate of 304.8 mmol h ⁻¹ g cat ⁻¹ at -0.9 V vs. RHE, surpassing the performance of both monometallic Cu and Zn catalysts. In situ spectroscopic analysis demonstrates that the Cu sites within CuZn facilitates the adsorption and activation of CO 2 and NO 3 ⁻ , while Zn sites additionally facilitate CO 2 adsorption and reduces the adsorption strength of *CO and *NH 2 on the catalyst surface, collectively promoting the formation of *CONH 2 as a key intermediate in urea synthesis. This study highlights the unique role of zinc in urea synthesis, offers new insights into optimizing the performance of copper-zinc catalysts, and serves as a valuable reference for future research on the role of zinc in urea synthesis.
研究领域:
电化学
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催化化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-10
·
IF 14.7
Tang Yirong,Jiang Zhan,Yuan Yubo,Xu Li,Jin Chuyao,Chen Bulin,Lin Zhichao,Zao Jie,Du Jianwei,Zhang Xiao,Gao Xiang,Liang Yongye
The electrocatalytic reduction of nitrogenous waste offers a sustainable approach to producing nitrogen-containing chemicals. The selective synthesis of high-value hydroxylamine (NH 2 OH) is challenging due to the instability of NH 2 OH as an intermediate. Here, we present a rational electrocatalyst design strategy for promoting NH 2 OH electrosynthesis by suppressing the competing pathways of further reduction. We screen zinc phthalocyanines (ZnPc) with a high energy barrier for NH 2 OH reduction by regulating their intrinsic activity. Additionally, we discover that carbon nanotube substrates exhibit significant NH 3 -producing activity, which can be effectively inhibited by the high coverage of ZnPc molecules. In-situ characterizations reveal that NH 2 OH and HNO are generated as intermediates in nitrate reduction to NH 3 , and NH 2 OH can be enriched in the ZnPc electrode. In the H-cell, the optimized ZnPc catalyst demonstrates a Faradaic efficiency (FE) of 53 ± 1.7% for NH 2 OH with a partial current density exceeding 270 mA cm −2 and a turnover frequency of 7.5 ± 0.2 s −1 . It also enables the rapid electrosynthesis of cyclohexanone oxime from nitrite with a FE of 64 ± 1.0%.
研究领域:
电化学
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催化
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Energy & Environmental Science
·
2021
·Vol. 15
·期 1
·234-243
·
IF 38.532
Xin Yu Zhang,Wen Jing Li,Xue Feng Wu,Yuan Wei Liu,Jiacheng Chen,Minhui Zhu,Hai Yang Yuan,Sheng Dai,Hai Feng Wang,Zheng Jiang,Peng Fei Liu,Hua Gui Yang
The electrosynthesis of valuable chemicals via carbon dioxide reduction reaction (CO2RR) has provided a promising way to address global energy and sustainability problems. However, the selectivity and activity of deep-reduction products (DRPs) still remain as big challenges. Here, a copper–carbon-based catalyst with a hydrophobic core–shell architecture has been constructed and was found to exhibit excellent DRPs of methane generation with a faradaic efficiency of 81 ± 3% in a neutral medium and a maximum partial current density of −434 mA cm−2 in a flow cell configuration, which is among the best of CO2-to-CH4 electrocatalysts. Density functional theory calculations suggest that the hydrophobic structure decreasing the water coverage on the catalyst surface can promote the protonation of the *CO intermediate and block CO production, further favoring the generation of methane. These results provide a new insight into the electrosynthesis of DRPs via constructing a hydrophobic core–shell architecture for tuning the surface water coverage.
研究领域:
化学工程
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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
Nature Synthesis
·
2024
·
IF 0
Huang Da-Shuai,Qiu Xiao-Feng,Huang Jia-Run,Mao Min,Liu Lingmei,Han Yu,Zhao Zhen-Hua,Liao Pei-Qin,Chen Xiao-Ming
The synthesis of urea by the electrochemical co-reduction of CO 2 and nitrate is a crucial and challenging task. Catalysts typically suffer from either low Faradaic efficiency (FE) or inadequate current density, leading to a restricted yield rate of urea. Here we report ultrasmall γ-Fe 2 O 3 nanoparticles (<2 nm) encapsulated in the pores of a conductive (40 S cm −1 ) metal–organic framework Ni-HITP (HITP = 2,3,6,7,10,11-hexaaminotriphenylene), resulting in a composite material, γ-Fe 2 O 3 @Ni-HITP. Under neutral conditions, γ-Fe 2 O 3 @Ni-HITP exhibited a state-of-art electrocatalytic performance for urea synthesis through the co-reduction of CO 2 and nitrate in CO 2 -saturated 1 M KHCO 3 and 0.1 M KNO 3 aqueous solutions, achieving a FE urea of 67.2(6)%, a current density of −90 mA cm −2 and an high yield rate of \(20.4(2)\,{\mathrm{g}}\,{\mathrm{h}}^{-1}\,{\mathrm{g}}_{\mathrm{cat}}^{-1}\) (7.7(1) mg h −1 cm −2 ), which is about five times higher than the rates of previously reported catalysts. No degradation was observed over 150 h of continuous operation at such a high yield rate. Enlarging the electrode area by 125 times yielded about 1.05(4) g of high-purity urea over 8 h. A mechanistic study revealed that Fe(III) ions in the γ-Fe 2 O 3 nanoparticles exhibit high activity, generating the key intermediates *NH 2 and *COOH. Furthermore, pairs of adjacent Fe(III) ions in the γ-Fe 2 O 3 nanoparticles can act as highly active catalytic sites for catalysing the C–N coupling between *NH 2 and *COOH, resulting in the formation of the subsequent key intermediate *CONH 2 , thereby contributing to the exceptionally high performance of γ-Fe 2 O 3 @Ni-HITP for urea production.
研究领域:
材料科学
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电化学
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催化化学
✓ 已验证
产品关联
DOI
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
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2022
·
IF 4.598
Mingran Li,Xia Qin,Mingxiao Gao,Tinghui Li,Yue Lv
Electrosynthesis of hydrogen peroxide (H 2 O 2 ) by two-electron oxygen reduction on the cathode is an attractive green approach for environmental remediation and chemical industries. In this study, an active carbon fiber (ACF) electrode modified with graphite carbon nitride (g-C 3 N 4 ) and carbon nanotubes (CNTs) is fabricated by a wet ultrasonic impregnation-calcination method. The doping content of g-C 3 N 4 , CNTs and polytetrafluoroethylene (PTFE) is optimized by response surface methodology (RSM). With optimum doping content, the H 2 O 2 generation by modified ACF increased several times, indicating the physicochemical and electronic transformation of ACF. The introduction of g-C 3 N 4 modulates the electronic structure of ACF, alleviating the adsorption energy of oxygen and coordinating the ∗ OOH binding capability. Besides reducing the oxygen adsorption energy, CNTs simultaneously improve the conductivity of electrodes. In addition, the addition of an appropriate amount of PTFE constructs a gas–liquid-solid three-phase equilibrium, facilitating oxygen diffusion. The effects of operating parameters on H 2 O 2 generation are also investigated and the optimal performance is achieved at current = 0.2 A, pH = 3, and aeration rate = 0.32 L/min. The modified ACF shows great potential in the practical applications for in-situ H 2 O 2 electro-generation.
研究领域:
环境科学
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材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
TRANSACTIONS OF TIANJIN UNIVERSITY
·
2025
·Vol. 31
·期 2
·65-73
·
IF 8.5
Dong Shengbin,Liu Qi,Gu Haoyuan,Wu Haoran,He Jing,Li Didi,Zhu Minghui
Carbon monoxide (CO) oxidation is crucial for pollutant removal and hydrogen purification. In recent years, copper–cerium (Cu–Ce)-mixed oxide catalysts have attracted significant attention due to their excellent activity and stability in CO oxidation. This study presents an innovative, environmentally friendly electrosynthesis method for producing stable, structured Cu–Ce catalysts in mesh form. This approach addresses the limitations of traditional pellet catalysts, such as fragility and poor thermal conductivity. The results demonstrated that incorporating cerium (Ce) enhanced the catalytic activity for CO oxidation threefold. A series of in situ characterizations revealed that the introduction of Ce led to the formation of a Cu–Ce mixed oxide solid solution, which significantly improved catalytic performance. Furthermore, higher pretreatment temperatures facilitated the decomposition of Ce compounds (nitrate and hydroxide), which promotes the formation of Cu–Ce solid solutions and increases the concentration of active intermediate species (Cu + ‒CO) during the reaction. This process ultimately enhanced the catalyst’s activity.
研究领域:
催化化学
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环境科学
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材料科学
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物理化学
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能源工程
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Ao Li,Jiran Li,Mengcheng Yin,Qizhen Zhang,Junhong Chen,Bozhong Pi,Minghao Bao,Changkun Song,Wei Shi,Chunpei Yu,Wenchao Zhang
The electrochemical synthesis of azo-bridged nitrogen-rich heterocyclic compounds has emerged as a promising strategy in the field of energetic materials due to its efficiency and controllability. Here, we present an innovative and environmentally benign electrocatalytic strategy employing cobalt phosphide (Co2P) nanowire arrays as cathodic catalysts for the safe and efficient synthesis of sodium 5,5′-azo-tetrazole under mild electrochemical conditions. Notably, the Co2P catalyst drives the reaction at a low potential of −0.4 V (vs Hg/HgO), which benefits from its unique needle-like morphology that optimizes electron transport pathways and active site distribution. By adjustment of the applied potential and reaction time, the yield of the reductive coupling can be effectively controlled. A detailed mechanistic pathway has been elucidated for the cathodic reductive coupling of sodium 5-nitrotetrazole mediated by Co2P electrodes. Electrochemical reduction at −0.6 V (vs Hg/HgO) and −0.8 V (vs Hg/HgO) yields a tunable mixture of sodium 5,5′-azo-tetrazole and its azoxy derivative, whereas exclusive generation of sodium 5,5′-azo-tetrazole is achieved at −1 V (vs Hg/HgO) through precise modulation of electron transfer kinetics. This voltage-gated synthesis paradigm establishes a novel electrochemical methodology for the programmable assembly of nitrogen-rich heterocyclic frameworks, offering unprecedented control over azo-linkage formation in energetic material design.
研究领域:
电化学
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材料科学
·
纳米技术
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有机合成
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能源材料
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Qiuying Wang,Zhiyuan Sang,Wei Liu,Zhenxin Li,Jun Li,Jiahuan Nie,Qichen Wang,De'an Yang,Feng Hou,Ji Liang
Industrial-level hydrogen peroxide (H 2 O 2 ) electrosynthesis is a promising alternative for the energy-intensive anthraquinone process. However, during repeated H 2 O 2 synthesis under harsh electrochemical conditions, active species could be leached away, undergo compositional segregation, or suffer from reconstruction, resulting in a loss in catalytic activity and efficiency. Besides, typical powder-form catalysts inevitably limit their performance enhancement, owing to the large interface resistance and peeling-off of powder catalysts from electrodes. Addressing these, a fine nickel particle catalyst that is with high-density defects and embedded in thin carbon substrates, via a rapid ultraviolet laser treatment, is reported. The high-density defects (i.e., twin boundaries, vacancies, and dislocations) in the Ni particles induce subtle and strong strain, which optimizes electrocatalytic activity and prevents catalyst deactivation effectively. By fabricating the catalyst into a free-standing form, the electronic conductivity and durability of the catalytic electrode can be significantly improved, therefore achieving stable H 2 O 2 production at an industrial-level current density of 250 mA cm −2 over 100 h with a Faradaic Efficiency of over 90% and a high yield of 4.27 mmol cm −2 h −1 . These results provide a promising pathway for the industrial and large-scale H 2 O 2 electrosynthesis, and highlight the potential application of electro-synthesized H 2 O 2 , such as rapid dye degradation.
研究领域:
材料科学
·
电化学工程
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催化化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）