CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Zhimin Song,Yan Liu,Jiankang Zhao,Yongzhi Zhong,Lang Qin,Qing Guo,Zhigang Geng,Jie Zeng
The electroreduction of N 2 into NH 3 is regarded as an environmentally-benign and sustainable strategy for artificial N 2 fixation at ambient conditions. Nevertheless, most of the catalysts suffer from low yield rate and Faradaic efficiency in this process. In this work, we developed a porous carbon with oxygen-containing groups (denoted as oxidized carbon) to promote N 2 electroreduction into NH 3 . At −0.3 V versus reversible hydrogen electrode ( vs RHE), oxidized carbon achieves a high Faradaic efficiency of 16.50% for NH 3 , which is 3.3 times as high as porous carbon (denoted as pristine carbon) (5.07%). Notably, the yield rate of oxidized carbon for NH 3 reaches 32.20 μg NH3 mg −1 cat. h −1 , higher than that (14.52 μg NH3 mg −1 cat. h −1 ) of pristine carbon at −0.5 V vs RHE. Mechanistic studies revealed that the introduction of oxygen-containing groups into porous carbon effectively decreased the energy barrier of hydrogenation and suppressed the competing hydrogen evolution reaction, thereby promoting N 2 electroreduction to NH 3 .
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2022
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IF 9.965
Kaiyue Gao,Chengming Zhang,Yi Zhang,Xiaoyu Zhou,Shuo Gu,Kehua Zhang,Xiufang Wang,Xiaojie Song
The conversion of N 2 to NH 3 is one of the most promising processes in maintaining natural life and chemical production. Photocatalytic nitrogen reduction reaction (NRR) has the advantage of clean and sustainable, which is considered to be an ideal synthesis technology. In this work, we report the successful synthesis of Bi 12 O 17 Br 2 ultrathin nanosheets through simple alkali treatment and solvothermal method . The Bi 12 O 17 Br 2 ultrathin nanosheets can improve the separation of carriers and the transfer of photogenerated electrons to N 2 molecules, thus improving the photocatalytic efficiency. Of note, the higher Bi/Br atomic ratio in Bi 12 O 17 Br 2 is beneficial to broaden the light absorption edge, and the high concentration of O atoms is easy to produce oxygen vacancies on the surface during the synthesis process of Bi 12 O 17 Br 2 . The abundant oxygen vacancies and high specific surface area enable N 2 molecules and water to have powerful chemical adsorption and activation. In addition, the photocatalytic reduction of N 2 to NH 3 in pure water shows excellent and stable performance, and the average generation rate of NH 3 reaches up to 620.5 μmol·L -1 ·h −1 . This study discovers that rich oxygen vacancies and ultrathin morphology may have a significant part in the process of the photocatalytic nitrogen reduction reaction.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Xiangchao Hui,Lifen Li,Qineng Xia,Song Hong,Leiduan Hao,Alex W. Robertson,Zhenyu Sun
The direct photochemical N 2 reduction reaction boasts the potential for clean and sustainable NH 3 manufacturing, yet achieving this remains a significant challenge. To activate and cleave the nonpolar N≡N bond and accelerate the transport and separation of charge carriers during photocatalysis , the design and facile synthesis of active, robust, cheap, and earth-abundant photocatalysts is crucial. Here, we demonstrate efficient and stable visible light fixation of N 2 to NH 3 by constructing a novel heterostructure consisting of two-dimensional Sb 2 O 3 nanosheets and one-dimensional W 18 O 49 nanowires . A remarkable NH 3 production rate of up to 731 μg NH3 h −1 g cat. −1 is attained in visible light over the nanocomposite without cocatalyst, 5.5-fold and 3.4-fold improvement over that of discrete Sb 2 O 3 and W 18 O 49 respectively, which also significantly exceeds many previous reported photocatalytic systems. The superior photocatalytic performance can be attributed to the unique structure of the composites, which provides ample exposed surface catalytic sites with a high density of oxygen vacancies, promoting the adsorption and activation of N 2 molecules to form *NNH. Equally importantly, the interface between Sb 2 O 3 and W 18 O 49 greatly facilitates charge carrier migration and separation. Further density functional theory calculations manifest that the interfacial metal sites on Sb 2 O 3 /W 18 O 49 serve as the main active centers which possess a strong donating electron ability to the empty N 2 antibonding orbitals to trigger the following NH 3 synthesis. This work provides a simple and effective method to modify metal oxides for enhancing N 2 photofixation.
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ADSORPTION SCIENCE & TECHNOLOGY
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2022
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IF 4.373
Zhijuan Zhang,Pengwei Li,Ting Zhao,Yuanhan Xia
The ZIF-8 crystals were successfully postsynthetically modified using methylamine (MA), ethylenediamine (ED), and N, N-dimethylethylenediamine (MMEN) to improve their adsorption performance toward CO2. Results showed that, compared with the original ZIF-8, the BET specific surface area of MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 has increased by 118.2%, 92.0%, and 29.8%, respectively. In addition, their total pore volume increased separately by 130.8%, 100%, and 48.7%. The adsorption capacities of CO2 on the amine-modified ZIF-8 samples followed the order . The CO2 adsorption capacities at 298 K on MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 were increased by 118.2%, 90.2%, and 29.8%, respectively. What is more, the CO2/N2 selectivities calculated using an IAST model of the amine@ZIF-8 samples at 0.01 bar and 298 K were also significantly improved and followed the order , which increased by 173.0%, 121.4%, and 22.6%, respectively. The isosteric heat of CO2 adsorption () on the MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 all becomes higher, while of N2 on these samples was slightly lower in comparison with that on the ZIF-8. Furthermore, after six recycle runs of gravimetric CO2 adsorption-desorption on MA-ZIF-8, the adsorption performance of CO2 is still very good, indicating that the MA-ZIF-8 sample has good regeneration performance and can be applied into industrial CO2 adsorption and separation.
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INORGANIC CHEMISTRY
·
2023
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IF 4.6
Naiyun Liu,Ruqiang Wu,Yixian Liu,Yunliang Liu,Peiji Deng,Yaxi Li,Yongchao Du,Yuanyuan Cheng,Zechao Zhuang,Zhenhui Kang,Haitao Li
Electrochemical nitrogen reduction reaction (NRR) is a promising method for ammonia synthesis under ambient conditions. However, the NRR performance is limited to an extremely strong N≡N bond in N2 and the competing hydrogen evolution reaction. Introducing oxygen vacancies (OVs) has been considered as a forceful means to accelerate the sluggish NRR reaction kinetics. Herein, we reported the design of Fe-doped NiMoO4 catalysts for NRR. Fe doping can increase the amount of OVs in the catalyst and contribute to lattice strain enhancement, thereby leading to the improvement of the electron transport rate and catalytic active for NRR. In 0.1 M Na2SO4 solution, the 5% Fe-NiMoO4 catalyst achieves a NH3 yield rate of 15.36 μg h–1 mgcat.–1 and a Faradaic efficiency of 26.85% under −0.5 V versus RHE. Furthermore, the 5% Fe-NiMoO4 catalyst exhibits excellent stability (up to 13 h) during the reaction.
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SEPARATION AND PURIFICATION TECHNOLOGY
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2023
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IF 8.6
Xuan Tang,Yugao Wang,Mengni Wei,Xueqin Zhang,Ye Li,Xiaomin Li,Jinping Li,Jiangfeng Yang
Reduction of zeolite crystal size from the micron scale to the nanoscale leads to a significant increase in specific surface area, favoring mass-transfer pathways. Here, we have prepared nanoscale (ca. 30–80 nm) IM-5@100 zeolite (IMF type) by a facile strategy of regulating the amount of Al source in the starting gel, and have investigated its CH 4 /N 2 adsorption and separation properties. We found that on decreasing the amount of Al source, the crystal size of the product changed significantly, decreasing from strips of length about 1 μm to irregular nanocrystals. Compared with micron-sized IM-5@50, the mesopore volume of IM-5@100 was increased fourfold from 0.12 cm 3 /g to 0.49 cm 3 /g, its external surface area was increased from 38 m 2 /g to 118 m 2 /g, and its DFT pore size distribution based on N 2 adsorption/desorption showed a mesopore distribution in the range 5–10 nm. Adsorption kinetics tests showed that nano-IM-5@100 can achieve adsorption equilibrium more swiftly and exhibits better mass-transfer performance. Moreover, IM-5@100 showed good adsorption capacity for CH 4 (17.8 cm 3 /g) and high IAST selectivity (4.7) for CH 4 /N 2 (50:50, v/v). Breakthrough experiments have indicated that IM-5@100 permits efficient practical separation of CH 4 /N 2 .
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JOURNAL OF ALLOYS AND COMPOUNDS
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2024
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IF 5.8
Ze Gao,Renming Liu,Daming Yang,Hongji Xu,Yuqi Wang,Bowen Li,Ming Feng,Ting Wang,Gangyong Jin
The adsorption and activation of N 2 as well as the competitive hydrogen evolution reaction (HER) pose significant challenges to the electrocatalytic nitrogen reduction reaction (ENRR), which severely limits its industrial application. Therefore, exploring the ENRR electrocatalysts with high activity and selectivity is an extremely important task. In this work, the oxygen vacancy-rich Fe 2 O 3 /Co 3 O 4 heterostructures (referred to as Vo-X-Fe 2 O 3 /Co 3 O 4 ) were rationally designed by employing Co 3 O 4 as a template via a simple hydrothermal and subsequent calcination method, which acted as highly efficient ENRR electrocatalysts. The electrocatalytic activity of Vo-X-Fe 2 O 3 /Co 3 O 4 can be easily regulated by optimization of the Fe content and the introduction of oxygen vacancy (Vo). The results demonstrate that the optimized Vo-1.0-Fe 2 O 3 /Co 3 O 4 catalyst achieves a high NH 3 yield of 47.37 μg h −1 mg cat −1 and a Faradaic efficiency (FE) of 22.42 %. Moreover, the excellent stability and reproducibility are also demonstrated. The comprehensive characterizations reveal that the exceptional performance of Vo-1.0-Fe 2 O 3 /Co 3 O 4 can be attributed to the improved N 2 adsorption and activation, restricted competitive HER and promoted electron transfer kinetics induced by the synergistic introduction of Vo and Fe. This work emerged a new speculating orientation for rational design of ENRR catalysts.
研究领域:
材料科学
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催化化学
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SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Zhaohao Li,Tianjing An,Jiaxi Yang,Dan Gao,Hongyuan Zhang,Heng Zhang
Capturing CO 2 from the flue gas in the power plant is an important measure to realize the low-carbon combustion of the fossil energy. This paper presents a novel technique which combines traditional methods of the chemical absorption, the physical adsorption and the membrane absorption. The ionic liquid ([TEPA][MIm]) is utilized to improve the CO 2 absorption performance and reduce the energy consumption. While the porous skeleton (ZIF-8) is added to the ionic liquid to reduce the viscosity while introducing the physical adsorption. Moreover, the hydrophobic ceramic membrane is utilized as the separation interface between the gas phase and the liquid phase, which can avoid the entrainment and overflow of the liquid phase while increasing the specific surface area. In terms of the material preparation and the characterization, the addition of ZIF-8 does not destroy the original chemical composition of [TEPA][MIm]. The average contact angle of the hydrophobic ceramic membrane is 140.55°, and the failure temperature is greater than 400 K, which conforms to the application situation of the power plant. In terms of the CO 2 capture and the desorption performance, the maximum CO 2 capture amount reaches 2.03 mol/mol. The temperature of complete desorption is 70 °C. Furthermore, the capture performance after five cycles can reach 80 % of the initial performance. The performance is better than that of the CO 2 capture technology utilizing the traditional monoethanolamine solution.
研究领域:
能源与环境工程
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材料科学
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JOURNAL OF MEMBRANE SCIENCE
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2024
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IF 8.4
Ziheng Li,Tiantian Li,Wenji Zheng,Xiangcun Li,Jiadong Zhu,Miao Yu,Xiaobin Jiang,Xuemei Wu,Gaohong He,Jianjun Zhang
The perfluorocarbons (PFCs), such as CF 4 , serving as crucial plasma etching gases, have caused a significant threat to the global greenhouse effect. Therefore, the enrichment and recycling of CF 4 is particularly important. However, since the CF 4 /N 2 mixture used for plasma etching with CF 4 content lower than 10 vol %, it is urgently necessary to develop N 2 -preferred transmissible membranes. Herein, cyclic crown ethers with hollow cavity were proposed to be encapsulated within ZIF-7 cages to sieving N 2 and CF 4 by “window-cage dual sieving”, while minimizing the sacrifice of N 2 permeance. Specifically, due to its larger size than the window size of ZIF-7, 15-crown-5 (15C5) was physically restricted into ZIF-7 cages, achieving permanent size sieving. As characterized by TEM and BET results, with the 15C5 modification ratio increasing, the ZIF-7 cage size was tuned from 0.46 nm to 0.43 nm, leading to improved N 2 /CF 4 selectivity. Meanwhile, the ether-oxygen bonding of 15C5 enhanced the interfacial compatibility between the 6FDA-DAM polymer matrix and ZIF-7, improving the filler loading as high as 50 wt%. The resultant 15C5 3 @ZIF-7/PI MMMs at filler loading of 40 wt% achieved N 2 permeability and N 2 /CF 4 ideal selectivity of up to 83.2 Barrer and 6.79, which were improved by 253.0 % and 223.3 %, compared to the pure PI membrane. Together with the good long-term stability and mechanical properties, 15C5@ZIF-7/PI MMMs provide a bright prospect in the membrane based recovery of PFCs for industrial applications.
研究领域:
材料科学
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环境科学
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Chem Catalysis
·
2026
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IF 10.7
Yuan Yuan,Xitang Qian,Shiyuan Liu,Weiwei Chen,Minglei Lu,Ernest Pahuyo Delmo,Yan Zhang,Yao Yao,Yuxiang Lyu,Yushen Liu,Dong Su,Minhua Shao
Efficient electrocatalytic nitrogen oxidation reaction (eNOR) requires promoting N 2 activation while minimizing the competing oxygen evolution reaction (OER). A compartmentalized La-ZnO core-shell electrocatalyst is constructed to mimic cellular functional segregation. The crystalline ZnO shell acts as a selective interface that enriches N 2 and limits OH − adsorption, thereby reducing the OER current. Beneath the shell, a porous amorphous oxygen-deficient core exposes dynamically accessible undercoordinated Zn–O–La sites. These sites promote stabilization of key intermediates, including ∗N 2 O 2 − , and support stepwise conversion after N 2 adsorption activation and oxidation. This spatial separation lowers the overall energetic demand along the 10-electron NOR pathway in alkaline electrolyte. The electrocatalyst reaches a Faradaic efficiency of 40.4% and a nitrate yield rate of 11.9 μmol mg −1 h −1 .
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RARE METALS
·
2026
·Vol. 45
·期 8
·e70421
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IF 12.1
Kun Huang,Jin Chen,Zhichao Miao,Jinglin Mu,Jianxun Yang,Fayuan Gang,Kang Ma,Yaohui Yao,Jin Zhou,Youqian Ding,Shengdong Zhang
en This link goes to a English section zh This link goes to a Chinese section Metallic cerium (Ce), a widely used surrogate for actinide metals, enables mechanistic studies of reactions in complex gas environments under controlled and safer laboratory conditions. Here, the oxidation behavior of Ce in H 2 O-N 2 mixed atmospheres was investigated from 200°C to 350°C using in situ thermogravimetry–mass spectrometry, in situ X-ray diffraction, intermediate capture, and first-principles calculations. A clear temperature-dependent switching of oxidation pathways was identified. At low temperatures (235°C), Ce undergoes direct steam oxidation to CeO 2 , while N 2 remains essentially inert. At high temperatures (300°C), the reaction proceeds mainly through a coupled nitridation–hydrolysis/oxidation route: N 2 participates, a transient CeN intermediate forms, and subsequent reaction with H 2 O yields CeO 2 accompanied by NH 3 evolution. The pathway switch is controlled by the structure and chemical state of cerium hydrides (CeH x ) generated at an early stage. Low-hydrogen, vacancy-rich CeH x (typified by CeH 2.29 /CeH 2 -like structures) exhibits enhanced surface reactivity that promotes N 2 adsorption, activation, and dissociation, thereby facilitating Ce nitridation to CeN. By contrast, hydrogen-rich CeH 2.97 /CeH 3 -like phases are limited by slow dehydrogenation and are ineffective in mediating N 2 activation. Although CeO 2 is the final product in both regimes, systematic differences in defect concentration and morphology indicate distinct controls on oxygen vacancy formation and particle growth kinetics. 摘要 en This link goes to a English section zh This link goes to a Chinese section 作为锕系金属的常用模拟金属,金属铈(Ce)可在受控且更安全的实验条件下开展复杂气体环境中的反应机理研究。本文利用原位热重-质谱联用、原位X射线衍射、反应中间体捕获以及第一性原理计算,研究了Ce在H 2 O-N 2 混合气氛和200°C–350°C范围内的氧化行为。结果表明氧化途径存在显著的温度依赖性切换:在低温区(235°C),Ce直接与水蒸气反应生成CeO 2 ,而N 2 基本呈惰性。在高温区(300°C),反应主要通过耦合的氮化-水解/氧化路径进行,金属Ce与N 2 反应形成CeN中间体,随后与H 2 O反应生成CeO 2 并释放NH 3 。氧化反应途径切换受早期阶段生成的氢化铈(CeH x )的结构与化学状态控制。低氢、富空位缺陷的CeH x (以CeH 2.29 /CeH 2 为典型)显示出更高的表面反应活性,可促进N 2 的吸附、活化与解离,从而有利于Ce氮化生成CeN。相比之下,富氢的CeH 2.97 /CeH 3 因脱氢速率较慢,难以有效活化N 2 。尽管两种反应路径的最终产物均为CeO 2 ,但缺陷浓度和形貌的系统性差异表明氧空位形成和CeO 2 颗粒生长动力学受不同氧化机制的控制。
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JOURNAL OF MEMBRANE SCIENCE
·
2026
·
IF 8.8
Xianjie Meng,Xinyue Meng,Jiayou Liao,Shouwei Liu,Chengyun Gao,Pengfei Li,Zhichao Zhai,Xu Wu
The recovery of low-concentration methane is crucial for both energy sustainability and greenhouse gas reduction. Membrane separation is an energy-efficient technology, but it still requires high-performance materials. We developed a novel mixed matrix membrane (MMM) by incorporating weakly polar Cu(INA) 2 nanoparticles into poly(styrene-ethylene-propylene-styrene) (SEPS). This design combined the mechanical strength of the SEPS skeleton with the specific adsorption capability of Cu(INA) 2 , achieving a synergistic effect. The obtained membrane utilized both dissolution-diffusion and adsorption-diffusion separation mechanisms, significantly enhancing CH 4 /N 2 separation performance. The CH 4 /N 2 ideal separation factor of 5 wt% Cu(INA) 2 /SEPS MMM reached 9.3, surpassing the majority of existing reports. Compared with pristine SEPS CH 4 /N 2 separation factor improved by 90%. In the CH 4 /N 2 (5/95, vol%) mixed gas test, the 5 wt% Cu(INA) 2 /SEPS MMM increased the CH 4 concentration from 5 vol% to 14.5 vol% and obtained a CH 4 /N 2 separation factor of 5.6. This work demonstrated an effective strategy for developing high-performance MMMs, which exhibited potential for the purification of low-concentration methane.
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