Chem Catalysis
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2022
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IF 0
Xianhao Zhang,Huijuan Jing,Shiming Chen,Bing Liu,Liang Yu,Jianping Xiao,Dehui Deng
Summary Cyclohexanone oxime (CHO), a key C=N organic compound in the manufacture of nylon 6, is conventionally synthesized via a multistep process that consumes expensive NH 3 and H 2 under harsh conditions. Herein, we report the direct electro-synthesis of CHO from low-cost NO, H 2 O, and cyclohexanone over a carbon catalyst under ambient conditions. A high Faradaic efficiency of 44.8% and a formation rate of 10.7 mg cm −2 h −1 for CHO were achieved at −0.4 V versus the reversible hydrogen electrode through optimizing the surface hydrophobicity of the catalyst to facilitate diffusion of reactants. Controlled experiments and 15 N-labeling tests verified that the nitrogen in the CHO product originates from NO. Density functional theory calculations showed that the armchair edge of carbon could be the active site with a reaction mechanism following NO → NO∗ → HNO∗ → HNOH∗ → NH 2 OH → CHO. This work suggests a direct, green, and low-cost synthesis strategy for high-value CHO from pollutant NO.
研究领域:
化学工程
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环境科学
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DOI
ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Ziqiang Wang,Zechuan Dai,Hongjie Yu,Hugang Zhang,Wenjing Tian,You Xu,Xiaonian Li,Liang Wang,Hongjing Wang
Electrochemical ammonia synthesis is considered as an alternative sustainable method to the traditional Haber–Bosch process because of the reduced energy consumption and mild operation conditions. The key is to design efficient electrocatalysts for facile adsorption and activation of nitrogen. Herein, a nanoporous Pd film with a tunable pore size has been in situ grown on Ni foam (nPd/NF) via a micelle-assisted replacement method using NF as a reductant and substrate, where polystyrene-b-poly(ethylene oxide) and 1,3,5-triisopropylbenzene serve as a pore-forming agent and a swelling agent, respectively. Combining the continuous large nanoporous structure and self-supported properties, the obtained nPd/NF exhibits excellent catalytic performance for ammonia synthesis with a high NH3 yield of 18.27 μg h–1 mgcat–1 and a faradaic efficiency of 10.36% in 0.1 M Na2SO4. This work provides a fascinating route for the rational design of self-supported porous noble metals with a tunable pore size for effective electrosynthesis of ammonia.
研究领域:
材料科学
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电化学
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催化化学
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DOI
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2024
·Vol. 99
·期 8
·1788-1799
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IF 2.8
Xinyu Han,Shiyu Yuan,Zhaolian Zhu,Jiawen Mei,Qiyuan Huang,Liya Ji,Hailing Wang
BACKGROUND Surface properties and adsorption performance of carbon materials play a crucial role in the electrochemical two-electron oxygen reduction to produce H 2 O 2 . However, there is still a lack of in-depth research on commercial carbon blacks in this area. Herein, four typical commercial carbon blacks (Acetylene black (AB), Ketjen black EC 600JD, Vulcan XC 72 and Black Pearls 2000) were used as cathode catalysts to generate H 2 O 2 . Surface chemistry and pore structure of electrodes of the four carbon blacks were systematically characterized, and their effects on H 2 O 2 adsorption, electrochemical generation and degradation were investigated. RESULTS Among the four carbon blacks, AB has the highest content of C–O–C/COOH and CO, which are active groups catalyzing the two-electron oxygen reduction reaction to generate H 2 O 2 . AB has the lowest level of defects and highest degree of graphitization, and AB-modified graphite felt electrode (AB-Ele) has the largest average pore diameter, smallest specific surface area and smaller charge transfer resistance. H 2 O 2 production using AB-Ele is the largest and reaches 567.7 mg L −1 at 180 min under a current density of 5 mA cm −2 , and only decreases by 17.6% after 10 repeated uses. CONCLUSION Overall, rich oxygen-containing functional groups such as C–O–C, COOH and CO, high degree of graphitization, suitable surface area and porosity as well as weak H 2 O 2 adsorption performance are beneficial for the two-electron oxygen reduction reaction to generate H 2 O 2 . AB-modified graphite felt electrode exhibits good catalytic activity and reusability in H 2 O 2 electrosynthesis, demonstrating promising application prospects. © 2024 Society of Chemical Industry (SCI).
研究领域:
化学工程
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材料科学
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环境科学
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产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Xinyu Liu,Bo Tang,Yang Gao,Xiaoyan Qi,Fengming Zhao,Zhaoyang Chen,Yinghong Zhu,Huajun Zheng,Youqun Chu
An efficient indirect electrosynthesis method for the preparation of 2,6-dichlorobenzonitrile has been developed, utilizing iodide ions as a redox mediator in the presence of acetate ions. The experimental results demonstrate that the addition of OAc − ions significantly influences the electrochemical behavior of I − ions, primarily through the complexation of OAc − ions with I 2 and I + species. This complexation facilitates the formation of [I 2 OAc] − ions, which are readily oxidized at the anode to generate I + ions. These I + ions are subsequently stabilized by OAc − ions, forming highly electrophilic [IOAc 2 ] − species. This mechanism leads to an enhanced yield of 2,6-dichlorobenzonitrile in the iodide-mediated indirect electrosynthesis reaction. Furthermore, compared to previous systems employing chloride ions, the present method exhibits a higher cyanation yield, indicating that [IOAc₂]⁻ ions possess superior electrophilic activity relative to [ICl₂]⁻ ions, thereby promoting the efficient cyanation of 2,6-dichlorobenzaldehyde. The method also demonstrates broad applicability, achieving good yields with various aromatic aldehydes. These findings highlight the potential of this approach for the synthesis of aromatic nitriles, particularly in the indirect electrosynthesis of nitriles from their corresponding aldehyde precursors. This work provides a promising strategy for the development of sustainable and efficient electrochemical synthesis methods in organic chemistry.
研究领域:
有机电化学
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电化学合成
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有机化学
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氧化还原化学
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氰化反应
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产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
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2023
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IF 4.6
Jin-Feng Jia,Tong Tong Hao,Pei-Hsuan Chen,Feng-Yi Wu,Wei Zhu,Sung-Fu Hung,Nian-Tzu Suen
Herein, we propose a simple yet effective method to deposit metal nanoparticles on Ti3C2Tx-MXene via direct electrosynthesis. Without using any reducing reagent or annealing under reducing atmosphere, it allows the conversion of metal salts (e.g., PtCl4, RuCl3·yH2O, IrCl3·zH2O, AgNO3, and CuCl2·2H2O) to metal nanoparticles with a small particle size (ca. 2 nm). Under these circumstances, it was realized that the support effect from Ti3C2Tx-MXene (electron pushing) is quite profound, in which the Ti3C2Tx-MXene support will act as an electron donor to push the electron to Pt nanoparticles and increase the electron density of Pt nanoparticles. It populates the antibonding state of Pt–Pt bonds as well as the adsorbate level that leads to a “weakening” of the ΔGH* in the optimal position. This rationalizes the outstanding activity of Pt/Ti3C2Tx-MXene (5 wt %, η10 = 16 mV) for the hydrogen evolution reaction (HER). In addition, this direct electrosynthesis method grants the growth of two or multiple types of metal nanoparticles on the Ti3C2Tx-MXene substrate that can perform dual or multiple functions as desired. For instance, one can prepare an electrocatalyst with Pt (2.5 wt %) and Ru nanoparticles (2.5 wt %) on the Ti3C2Tx-MXene support from the same synthetic method. This electrocatalyst (Pt_Ru/Ti3C2Tx-MXene) can display good electrocatalytic HER performance in both acid (0.5 M H2SO4) and alkaline electrolytes (1.0 M KOH).
研究领域:
材料科学
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电化学
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催化
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DOI
PubMed
高影响因子
JOM
·
2020
·Vol. 72
·期 11
·3887-3894
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IF 2.054
Pang Zhongya,Zou Xingli,Tang Wei,Shi Tianyu,Wang Shujuan,Ji Li,Hsu Hsien-Yi,Xu Qian,Lu Xionggang
Carbide-derived carbon (CDC) as an unconventional porous carbon material has been widely used for various applications. In this work, Ti 3 AlC 2 -derived porous carbon (Ti 3 AlC 2 -CDC) was electrochemically synthesized at 900°C and 3.0 V in molten CaCl 2 -NaCl. The obtained Ti 3 AlC 2 -CDC with abundant slit-like mesopores showed a high specific surface area of 425 m 2 /g. The variation of the morphology from the Ti 3 AlC 2 precursor to Ti 3 AlC 2 -CDC was investigated, with the Ti 3 AlC 2 -CDC demonstrating a typical loose layered morphology and amorphous carbon structure. The intermediate products were also systematically analyzed to investigate the molten salt electrochemical etching process. It was found that Ti 3 AlC 2 can be oxidized by residual O 2− in the molten salt to form tiny Al 2 O 3 particles on the anodic Ti 3 AlC 2 surface during the etching process, then Ti 3 AlC 2 -CDC can be obtained by successively removing these Al 2 O 3 , Al, and Ti from the Ti 3 AlC 2 precursor.
研究领域:
材料科学
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电化学
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纳米材料
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能源材料
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表面工程
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DOI
高影响因子
CATALYSIS LETTERS
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2024
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IF 2.3
Xu Pengfei,Ma Haiming,Shen Wenjuan,Quan Fengjiao,Li Jianfen,He Yun
Ammonia (NH 3 ) can be used as a fertilizer, a chemical or a new generation of fuel and has important agricultural and industrial value. Electrochemical NO 3 – -to-NH 3 (NITRR) can realize the conversion of waste into treasure and waste resources, which is a promising method for ammonia synthesis. However, the process of NITRR is very complicated, resulting in product diversification and poor selectivity. In this work, an iron modified cerium oxide in rod form (Fe/CeO 2 -rod) catalysts was designed and used for the NITRR. The Fe/CeO 2 -rod catalyst showed excellent activity, and achieves high Faradaic efficiency (FE 95%) and NH 3 yield rate (4.04 mg h –1 cm –2 ) in 0.1 M KOH electrolyte at – 0.52 V versus reversible hydrogen electrode. Furthermore, this catalyst exhibits a negligible activity decay during continuous electrolysis for 25 h. Further experiments provide the important role of Fe, which promote the formation of hydrogen radicals (H*). This study may provide new pathways to improve the activity of inexpensive catalysts for NITRR. Graphical Abstract
研究领域:
化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale
·
2021
·Vol. 13
·期 15
·7381-7388
·
IF 7.79
He Xiao,Xiaoling Du,Man Zhao,Ya Li,Tianjun Hu,Haishun Wu,Jianfeng Jia,Nianjun Yang
The integration of black phosphorus (BP) with metal phosphides is known to produce high-performance electrocatalysts for oxygen evolution reduction (OER), although increased stability and prevention of the degradation of their lone pairs would be desirable improvements. In this work, cobalt phosphide (CoP)/BP heterostructures were electrochemically synthesized with a two-electrode system, where cobalt ions were generated in situ at a Co anode, and non-aggregated BP nanosheets (NSs) were exfoliated from the bulky BP cathode. With an electrolysis voltage of 30 V, the CoP/BP heterostructure exhibited a superior and stable OER performance (e.g., an overpotential of 300 mV at 10 mA cm−2, which is 41 mV lower than that obtained with a RuO2 catalyst). The CoOx formed in situ during the OER catalysis and remaining CoP synergistically contributed to the enhanced OER performance. The present strategy provides a new electrosynthetic method to prepare stable BP electrocatalysts and also further expands their electrochemical applications.
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
CHEMISTRY-A EUROPEAN JOURNAL
·
2019
·Vol. 25
·期 23
·5904-5911
·
IF 5.16
Guoqiang Liu,Zhiqing Cui,Miaomiao Han,Shengbo Zhang,Cuijiao Zhao,Chun Chen,Guozhong Wang,Haimin Zhang
Graphical Room at the active site : A room-temperature redox approach is used to prepare a composite core–shell-structured Au@CeO 2 electrocatalyst (see figure) composed of small gold nanoparticles (<10 nm) and rich oxygen vacancies in CeO 2 nanoparticles to synergistically boost the electrocatalytic activity toward the N 2 reduction reaction (NRR) to NH 3 . Electrosynthesis of NH 3 through the N 2 reduction reaction (NRR) under ambient conditions is regarded as promising technology to replace the industrial energy- and capital-intensive Haber–Bosch process. Herein, a room-temperature spontaneous redox approach to fabricate a core–shell-structured Au@CeO 2 composite, with Au nanoparticle sizes below about 10 nm and a loading amount of 3.6 wt %, is reported for the NRR. The results demonstrate that as-synthesized Au@CeO 2 possesses a surface area of 40.7 m 2 g −1 and a porous structure. As an electrocatalyst, it exhibits high NRR activity, with an NH 3 yield rate of 28.2 μg h −1 cm −2 (10.6 μg h −1 mg −1 cat. , 293.8 μg h −1 mg −1 Au ) and a faradaic efficiency of 9.50 % at −0.4 V versus a reversible hydrogen electrode in 0.01 m H 2 SO 4 electrolyte. The characterization results reveal the presence of rich oxygen vacancies in the CeO 2 nanoparticle shell of Au@CeO 2 ; these are favorable for N 2 adsorption and activation for the NRR. This has been further verified by theoretical calculations. The abundant oxygen vacancies in the CeO 2 nanoparticle shell, combined with the Au nanoparticle core of Au@CeO 2 , are electrocatalytically active sites for the NRR, and thus, synergistically enhance the conversion of N 2 into NH 3 .
研究领域:
化学
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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 Physical Chemistry C
·
2019
·
IF 4.309
Liudi Ji,Junxing Hao,Kangbing Wu,Nianjun Yang
Properties of metal–organic frameworks (MOFs) are determined by metal centers, organic ligands, and applied synthesis methods. For electrosynthesis of MOFs, the applied potential is expected to play a key role in determining the morphology, thickness, electrochemical properties, and applications of MOFs. Herein, Cu-BTC (H3BTC: 1,3,5-benzenetricarboxylic acid) films are electrosynthesized at different cathodic potentials. They feature different morphologies, thicknesses, and amounts of active copper centers, although they do show similar bonding properties, chemical compositions, phase purity, crystallinity, and surface electronic states of copper centers. Using nicotine amide adenine dinucleotide, the sensing application of these Cu-BTC films is explored, showing potential-dependent catalytic ability. Further monitoring of six other organic compounds (herein xanthine, hypoxanthine, diethylstilbestrol, estradiol, sunset yellow, and tartrazine) reveals the morphology and thickness of Cu-BTC films and the amount of copper centers inside these Cu-BTC films determines the accumulation or sensing ability of Cu-BTC films. Highly sensitive detection of these molecules individually and simultaneously is achieved with Cu-BTC electrosynthesized at −1.30 V. Electrosynthesized Cu-BTC films are thus excellent electrode materials for sensitive sensing of various analytes.
研究领域:
材料科学
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分析化学
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产品关联
DOI
高影响因子
IONICS
·
2023
·
IF 2.8
Li Wei,Zhao Yi,Zhang Chunyan,Kang Juanxue,Tang Qinyuan,Liu Yongfei,Yang Lin,Yuan Shutang
The production of hydrogen peroxide (H 2 O 2 ) by 2-electron oxygen reduction reaction (ORR) in acidic electrolytes is a promising alternative to the existing anthraquinone process. However, the development of cost-effective catalysts with high activity for H 2 O 2 electrosynthesis remains a great challenge. Here, we report a cobalt-nitrogen-carbon catalyst in which cobalt single atoms are supported on carbon black (Co-N-CB) for the electrosynthesis of H 2 O 2 in an acid medium. The prepared Co-N-CB shows high activity for O 2 reduction into H 2 O 2 with an average selectivity of 80.6% over a wide potential range of 0.1–0.7 V vs. RHE in 0.1 M HClO 4 electrolytes. We found that (i) the Co single atoms are the active sites of 2-electron ORR; (ii) a catalyst for efficient H 2 O 2 production by O 2 reduction should achieve a good balance between high ORR activity and H 2 O 2 selectivity. Using Co-N-CB as a cathodic catalyst, the electrochemical device could electrosynthesize H 2 O 2 directly from H 2 and O 2 with a high productivity of 291.0 mol kg cat −1 h −1 . Our work provides a flexible way to prepare affordable catalysts for efficient H 2 O 2 electrosynthesis.
研究领域:
材料科学
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催化化学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Synthesis
·
2025
·
IF 20
Wang Ruizhao,Dai Jie,Zhao Long,Hu Zhiwei,Chen Chien-Te,Kuo Chang-Yang,Zhan Guangming,Shi Yanbiao,Wang Jiaxian,Zou Yunjie,Xu Mingkai,Zou Xingyue,Zheng Qian,Zhou Bing,Wang Kaiyuan,Zhao Rui,Zhang Yan,Shen Yunhao,Yao Yancai,Zhang Lizhi
Electrochemical O 2 activation offers a green approach for efficient synthesis of singlet oxygen ( 1 O 2 ). However, it is commonly determined by adsorption-dependent O 2 activation and transformation and can suffer from the sluggish desorption of surface-bound *OOH. Here we report an adsorption-independent O 2 activation pathway for 1 O 2 electrosynthesis via an O 2 mono-hydrogenation process on compressive-strained rutile TiO 2 (CSR-TiO 2 ). This CSR-TiO 2 achieved an 1 O 2 generation rate of 148.26 μmol l −1 min −1 with near 100% Faradaic efficiency, outperforming the strain-free counterpart (35.97 μmol l −1 min −1 ) and other previously reported materials. Such superior performance of CSR-TiO 2 stemmed from compressive strain, which can suppress the formation of reductive unsaturated sites for the O 2 adsorption and enhance the reductive ability of atomic hydrogen (H*), favouring the O 2 mono-hydrogenation pathway and bypassing the traditional surface-bound *OOH desorption pathway. The generated 1 O 2 could be utilized for the selective oxidation of thioanisole and its derivatives, offering a promising strategy for green organic synthesis.
研究领域:
材料科学
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电化学
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绿色合成
✓ 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）