In this work, 44 metal–organic frameworks (MOFs) are screened for efficient electrocatalytic nitrogen reduction reaction (eNRR). The isosteric heats of N2 adsorption on the 44 metal active centers of MOFs are calculated by the grand canonical Monte Carlo method. It is found that p-block-elements exhibit the highest N2 affinity among all screened elements, implying their excellent catalytic potentials for eNRR. Furthermore, the Al element is preferentially chosen as the metal center of MOFs (MIL-53 (Al)) owing to its relatively low toxicity and cost. Combined in situ Diffuse Reflectance Infrared Fourier Transform (DRIFT) analysis with theoretical calculation, we found that N2 is mainly attracted by the bridging oxygen of Al-O-Al structure in the MIL-53 (Al). The optimized MIL-53 (Al) shows a superior activity with the NH3 yield rate of 74.55 ± 1 μg h−1 mgcat−1 at −0.3 V vs. Reversible Hydrogen Electrode (RHE), to our best knowledge, which is currently the highest activity of MOF-based catalyst for eNRR reported in the literature.
在这项工作中，筛选了44种金属有机框架（MOFs）用于高效的电催化氮还原反应（eNRR）。用大正则蒙特卡罗方法计算了mof的44个金属活性中心的N2吸附等容热。结果表明，在所有筛选的元素中，p-块元素对N2的亲和力最高，这表明它们具有良好的eNRR催化潜力。此外，由于MIL-53 （Al）的毒性和成本相对较低，因此优先选择Al元素作为mof的金属中心。结合原位漫反射红外傅里叶变换（DRIFT）分析和理论计算，发现MIL-53 （Al）中N2主要被Al- o -Al结构的桥接氧所吸引。优化后的MIL-53 （Al）在−0.3 V下的NH3产率为74.55±1 μg h−1 mgcat−1，是目前文献报道的mof基eNRR催化剂中活性最高的。
{"title":"Screening of metal–organic frameworks for efficient electrocatalytic nitrogen reduction","authors":"Jiawei Lin, Yuhang Li, Hongping Yan, Tingting Qi, Shijing Liang, Lilong Jiang","doi":"10.1002/aic.18652","DOIUrl":"https://doi.org/10.1002/aic.18652","url":null,"abstract":"In this work, 44 metal–organic frameworks (MOFs) are screened for efficient electrocatalytic nitrogen reduction reaction (eNRR). The isosteric heats of N<sub>2</sub> adsorption on the 44 metal active centers of MOFs are calculated by the grand canonical Monte Carlo method. It is found that p-block-elements exhibit the highest N<sub>2</sub> affinity among all screened elements, implying their excellent catalytic potentials for eNRR. Furthermore, the Al element is preferentially chosen as the metal center of MOFs (MIL-53 (Al)) owing to its relatively low toxicity and cost. Combined <i>in situ</i> Diffuse Reflectance Infrared Fourier Transform (DRIFT) analysis with theoretical calculation, we found that N<sub>2</sub> is mainly attracted by the bridging oxygen of Al-O-Al structure in the MIL-53 (Al). The optimized MIL-53 (Al) shows a superior activity with the NH<sub>3</sub> yield rate of 74.55 ± 1 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> at −0.3 V vs. Reversible Hydrogen Electrode (RHE), to our best knowledge, which is currently the highest activity of MOF-based catalyst for eNRR reported in the literature.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"1 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Runci Song, Kefeng Fang, Bing Xiang, Luchang Han, Xin Feng, Jie Chen, Chao Yang
The collision between bubbles is essential to gas–liquid dispersion systems. When bubbles encounter each other, they may either rebound or coalesce. Yet, little is known about the rebound dynamics immediately after two bubbles collide. This work investigates such collision dynamics of two bubbles at high Reynolds numbers in water through experiment and simulation. The moving velocity, deformation, contact time during collision and restitution coefficient of bubbles are analyzed. Simulations reproduced quantitatively the bubble rebound behavior, revealing the evolution of various energies involved in collision. Simulation results show that over 70% of the system's initial mechanical energy (SME) could be converted into bubble surface energy (BSE) during the approach. In turn, the excess BSE is converted back into SME driving bubbles to rebound with significant dissipation. A mass-spring-damper model is developed, which describes the dynamic of bubble rebound well. This contribution enhances the understanding of bubble interactions in multiphase flow.
{"title":"Dynamics of two bubbles colliding at high Reynolds numbers in water: Bubble rebound behavior study","authors":"Runci Song, Kefeng Fang, Bing Xiang, Luchang Han, Xin Feng, Jie Chen, Chao Yang","doi":"10.1002/aic.18682","DOIUrl":"https://doi.org/10.1002/aic.18682","url":null,"abstract":"The collision between bubbles is essential to gas–liquid dispersion systems. When bubbles encounter each other, they may either rebound or coalesce. Yet, little is known about the rebound dynamics immediately after two bubbles collide. This work investigates such collision dynamics of two bubbles at high Reynolds numbers in water through experiment and simulation. The moving velocity, deformation, contact time during collision and restitution coefficient of bubbles are analyzed. Simulations reproduced quantitatively the bubble rebound behavior, revealing the evolution of various energies involved in collision. Simulation results show that over 70% of the system's initial mechanical energy (SME) could be converted into bubble surface energy (BSE) during the approach. In turn, the excess BSE is converted back into SME driving bubbles to rebound with significant dissipation. A mass-spring-damper model is developed, which describes the dynamic of bubble rebound well. This contribution enhances the understanding of bubble interactions in multiphase flow.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"21 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760822","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Producing battery-grade Li2CO3 product from salt-lake brine is a critical issue for meeting the growing demand of the lithium-ion battery industry. Traditional procedures include Na2CO3 precipitation and multi-stage crystallization for refining, resulting in significant lithium loss and undesired lithium product quality. Herein, we first proposed a bipolar membrane CO2 mineralization technique for directly producing battery-grade Li2CO3 from lake brine that enriches alkali metals (Na+, K+). Results indicate the process can successfully separate Li+ from contaminants and present a selectivity above 900 for Li+ through the CO2 mineralization reaction, while prevent electro-oxidating Cl− to Cl2 pollution. The obtained Li2CO3 production purity is above 99.75% with lithium recovery rate of 86%. Carbon dioxide was captured in the form of Li2CO3, with a capacity of 595 g of CO2 for1 kg of Li2CO3. The technology provides a sustainable and cost-effective path for producing battery-grade Li2CO3 from the lake brine.
{"title":"Producing battery grade lithium carbonate from salt-lake brine via bipolar membrane carbon dioxide mineralization","authors":"Weixiang Shan, Guangzhong Cao, Tianle Gu, Xiao Liu, Dongyue Sun, Rongqiang Fu, Zhaoming Liu, Chenxiao Jiang, Tongwen Xu","doi":"10.1002/aic.18675","DOIUrl":"https://doi.org/10.1002/aic.18675","url":null,"abstract":"Producing battery-grade Li<sub>2</sub>CO<sub>3</sub> product from salt-lake brine is a critical issue for meeting the growing demand of the lithium-ion battery industry. Traditional procedures include Na<sub>2</sub>CO<sub>3</sub> precipitation and multi-stage crystallization for refining, resulting in significant lithium loss and undesired lithium product quality. Herein, we first proposed a bipolar membrane CO<sub>2</sub> mineralization technique for directly producing battery-grade Li<sub>2</sub>CO<sub>3</sub> from lake brine that enriches alkali metals (Na<sup>+</sup>, K<sup>+</sup>). Results indicate the process can successfully separate Li<sup>+</sup> from contaminants and present a selectivity above 900 for Li<sup>+</sup> through the CO<sub>2</sub> mineralization reaction, while prevent electro-oxidating Cl<sup>−</sup> to Cl<sub>2</sub> pollution. The obtained Li<sub>2</sub>CO<sub>3</sub> production purity is above 99.75% with lithium recovery rate of 86%. Carbon dioxide was captured in the form of Li<sub>2</sub>CO<sub>3</sub>, with a capacity of 595 g of CO<sub>2</sub> for1 kg of Li<sub>2</sub>CO<sub>3</sub>. The technology provides a sustainable and cost-effective path for producing battery-grade Li<sub>2</sub>CO<sub>3</sub> from the lake brine.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"388 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Large language models (LLMs) are often criticized for lacking true “understanding” and the ability to “reason” with their knowledge, being seen merely as autocomplete engines. I suggest that this assessment might be missing a nuanced insight. LLMs do develop a kind of empirical “understanding” that is “geometry”-like, which is adequate for many applications. However, this “geometric” understanding, built from incomplete and noisy data, makes them unreliable, difficult to generalize, and lacking in inference capabilities and explanations. To overcome these limitations, LLMs should be integrated with an “algebraic” representation of knowledge that includes symbolic AI elements used in expert systems. This integration aims to create large knowledge models (LKMs) grounded in first principles that can reason and explain, mimicking human expert capabilities. Furthermore, we need a conceptual breakthrough, such as the transformation from Newtonian mechanics to statistical mechanics, to create a new science of LLMs.
{"title":"Do large language models “understand” their knowledge?","authors":"Venkat Venkatasubramanian","doi":"10.1002/aic.18661","DOIUrl":"https://doi.org/10.1002/aic.18661","url":null,"abstract":"Large language models (LLMs) are often criticized for lacking true “understanding” and the ability to “reason” with their knowledge, being seen merely as autocomplete engines. I suggest that this assessment might be missing a nuanced insight. LLMs do develop a kind of empirical “understanding” that is “geometry”-like, which is adequate for many applications. However, this “geometric” understanding, built from incomplete and noisy data, makes them unreliable, difficult to generalize, and lacking in inference capabilities and explanations. To overcome these limitations, LLMs should be integrated with an “algebraic” representation of knowledge that includes symbolic AI elements used in expert systems. This integration aims to create large knowledge models (LKMs) grounded in first principles that can reason and explain, mimicking human expert capabilities. Furthermore, we need a conceptual breakthrough, such as the transformation from Newtonian mechanics to statistical mechanics, to create a new science of LLMs.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"18 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Microbubbles have been widely applied in various fields. Here, an oscillating feedback microreactor (OFM) was designed to produce microbubbles at high throughput (5–80 mL/min), where the hydrodynamics and mass transfer performance of gas–liquid two-phase system were investigated. The hydrodynamics results showed that three secondary flows (oscillation, vortex, and feedback) could be effectively generated for inducing chaotic flow in the OFM, and the gas phase could be effectively broken up into small microbubbles. The bubble size was more sensitive to the liquid phase flow rate than the gas phase. Two dimensionless prediction formulas for bubble Sauter size were proposed based on gas–liquid flow ratio and Reynolds number at different liquid flow rates. The mass transfer experiments showed that the volumetric average mass transfer coefficient kLa was 1–3 orders of magnitude higher than those of conventional reactors.
{"title":"Hydrodynamics and mass transfer performance of gas–liquid two-phase flow in a high-throughput chaotic microreactor","authors":"Jia-Ni Zhang, Hao-Tian Tong, Zu-Chun Shi, Ting-Liang Xie, Qiang Liu, Shi-Xiao Wei, Shuang-Feng Yin","doi":"10.1002/aic.18657","DOIUrl":"https://doi.org/10.1002/aic.18657","url":null,"abstract":"Microbubbles have been widely applied in various fields. Here, an oscillating feedback microreactor (OFM) was designed to produce microbubbles at high throughput (5–80 mL/min), where the hydrodynamics and mass transfer performance of gas–liquid two-phase system were investigated. The hydrodynamics results showed that three secondary flows (oscillation, vortex, and feedback) could be effectively generated for inducing chaotic flow in the OFM, and the gas phase could be effectively broken up into small microbubbles. The bubble size was more sensitive to the liquid phase flow rate than the gas phase. Two dimensionless prediction formulas for bubble Sauter size were proposed based on gas–liquid flow ratio and Reynolds number at different liquid flow rates. The mass transfer experiments showed that the volumetric average mass transfer coefficient <i>k</i><sub>L</sub><i>a</i> was 1–3 orders of magnitude higher than those of conventional reactors.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"12 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756267","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Suhan Liu, Gongli Wu, Yuqing Chen, Yaoyao Han, Mingchao Zhang, Jincan Kang, Min Tang, Krijn P. de Jong, Qinghong Zhang, Ye Wang, Kang Cheng
The direct and selective conversion of syngas into C2+ oxygenates is challenging due to the complex reaction network. Here, we report a robust relay system for the direct synthesis of methyl acetate (MA) from syngas, which combines CuZnAlOx/H-ZSM-5 for syngas to dimethyl ether (DME) with modified H-MOR for DME carbonylation. The dehydration of methanol to DME on H-ZSM-5 significantly enhanced the hydrogenation of CO on CuZnAlOx, because of high DME equilibrium yields. Blocking of Brönsted acid sites with basic molecules or selective dealumination of 12-membered rings in H-MOR suppressed the zeolite coking. Besides, reaction temperatures above 240°C avoided H2O poisoning of carbonylation sites inside 8-MR side pockets of H-MOR, further benefiting the catalytic stability. Eventually, this relay system provided a high MA selectivity of 75% and an acetic acid selectivity of 13% at a CO conversion of 65%, outperforming reported catalysts.
{"title":"Direct conversion of syngas into methyl acetate by relay catalysis: From fabrication of active sites to process control","authors":"Suhan Liu, Gongli Wu, Yuqing Chen, Yaoyao Han, Mingchao Zhang, Jincan Kang, Min Tang, Krijn P. de Jong, Qinghong Zhang, Ye Wang, Kang Cheng","doi":"10.1002/aic.18664","DOIUrl":"https://doi.org/10.1002/aic.18664","url":null,"abstract":"The direct and selective conversion of syngas into C<sub>2+</sub> oxygenates is challenging due to the complex reaction network. Here, we report a robust relay system for the direct synthesis of methyl acetate (MA) from syngas, which combines CuZnAlO<sub><i>x</i></sub>/H-ZSM-5 for syngas to dimethyl ether (DME) with modified H-MOR for DME carbonylation. The dehydration of methanol to DME on H-ZSM-5 significantly enhanced the hydrogenation of CO on CuZnAlO<sub><i>x</i></sub>, because of high DME equilibrium yields. Blocking of Brönsted acid sites with basic molecules or selective dealumination of 12-membered rings in H-MOR suppressed the zeolite coking. Besides, reaction temperatures above 240°C avoided H<sub>2</sub>O poisoning of carbonylation sites inside 8-MR side pockets of H-MOR, further benefiting the catalytic stability. Eventually, this relay system provided a high MA selectivity of 75% and an acetic acid selectivity of 13% at a CO conversion of 65%, outperforming reported catalysts.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"26 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Supported metal catalysts have been widely applied and commonly fabricated through the H2 reduction process. Herein, we develop a H2-free room-temperature discharge-driven reduction (RT-DR) reactor for fabricating supported metal catalysts at room temperature without H2. By RT-DR reactor, a catalyst with pseudo-boehmite (PB) as support (CdS/Pt/PB) is fabricated. In visible-light-driven photocatalytic H2O splitting to H2, CdS/Pt/PB shows a H2 evolution rate of 1132 μmol h−1, which is greatly enhanced than that on catalyst prepared by traditional H2-reduction (633 μmol h−1). RT-DR reactor is also used to prepare a catalyst with low sodium PB (LSPB) as support (CdS/Pt/LSPB). In visible-light-driven photocatalytic H2O splitting to H2, CdS/Pt/LSPB shows a H2 evolution rate of 2554 μmol h−1, which is 2.5 times higher than that on catalyst prepared by traditional H2-reduction (1029 μmol h−1). Thus, RT-DR reactor has high efficiency and universality in preparing catalysts, thus offering a great potential for commercialization.
{"title":"Discharge reactor for fabricating efficient supported metal catalysts at room temperature in the absence of H2","authors":"Peng Liu, Xin-Yu Meng, Xujun Wang, Yiyi Zhao, Yu-Long Men, Yun-Xiang Pan","doi":"10.1002/aic.18669","DOIUrl":"https://doi.org/10.1002/aic.18669","url":null,"abstract":"Supported metal catalysts have been widely applied and commonly fabricated through the H<sub>2</sub> reduction process. Herein, we develop a H<sub>2</sub>-free room-temperature discharge-driven reduction (RT-DR) reactor for fabricating supported metal catalysts at room temperature without H<sub>2</sub>. By RT-DR reactor, a catalyst with pseudo-boehmite (PB) as support (CdS/Pt/PB) is fabricated. In visible-light-driven photocatalytic H<sub>2</sub>O splitting to H<sub>2</sub>, CdS/Pt/PB shows a H<sub>2</sub> evolution rate of 1132 μmol h<sup>−1</sup>, which is greatly enhanced than that on catalyst prepared by traditional H<sub>2</sub>-reduction (633 μmol h<sup>−1</sup>). RT-DR reactor is also used to prepare a catalyst with low sodium PB (LSPB) as support (CdS/Pt/LSPB). In visible-light-driven photocatalytic H<sub>2</sub>O splitting to H<sub>2</sub>, CdS/Pt/LSPB shows a H<sub>2</sub> evolution rate of 2554 μmol h<sup>−1</sup>, which is 2.5 times higher than that on catalyst prepared by traditional H<sub>2</sub>-reduction (1029 μmol h<sup>−1</sup>). Thus, RT-DR reactor has high efficiency and universality in preparing catalysts, thus offering a great potential for commercialization.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"74 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhenbin Gu, Jinkun Tan, Haoli Zhou, Zhengkun Liu, Lin Ge, Guangru Zhang, Wanqin Jin
A raw hydrogen mixture frequently results in a reduction in conversion efficiency and the generation of undesired by-products. The application of advanced membrane technology has the potential to offer an economically viable solution for the recovery of hydrogen from such mixtures. BaZr1−x−yCexYyO3−δ is increasingly regarded as an optimal perovskite hydrogen permeable membrane. Nevertheless, the main drawback to its use in a larger scale is the extremely low hydrogen permeability and stability. An original perovskite material is proposed in this study, BaZr0.7Ce0.2Y0.1O3−δ-Fx. A thermodynamic-controlled sintering strategy (TCS) has been employed to inhibit the evaporation of metals from ceramic solids. The TCS directly caused the hydrogen permeation flux to reach 1.07 ml·min−1 cm−2, representing a fourfold improvement. Furthermore, F-doping demonstrated enhanced performance at low and medium temperatures. The aforementioned successful strategy provides an effective path for the tailoring of perovskite materials and promotes its application for the industrial-scale separation of hydrogen.
{"title":"High H2 permeability in F-doped BaZr0.7Ce0.2Y0.1O3−δ perovskite membranes via thermodynamic controlled sintering","authors":"Zhenbin Gu, Jinkun Tan, Haoli Zhou, Zhengkun Liu, Lin Ge, Guangru Zhang, Wanqin Jin","doi":"10.1002/aic.18670","DOIUrl":"https://doi.org/10.1002/aic.18670","url":null,"abstract":"A raw hydrogen mixture frequently results in a reduction in conversion efficiency and the generation of undesired by-products. The application of advanced membrane technology has the potential to offer an economically viable solution for the recovery of hydrogen from such mixtures. BaZr<sub>1−x−y</sub>Ce<sub>x</sub>Y<sub>y</sub>O<sub>3−δ</sub> is increasingly regarded as an optimal perovskite hydrogen permeable membrane. Nevertheless, the main drawback to its use in a larger scale is the extremely low hydrogen permeability and stability. An original perovskite material is proposed in this study, BaZr<sub>0.7</sub>Ce<sub>0.2</sub>Y<sub>0.1</sub>O<sub>3−δ</sub>-F<sub>x</sub>. A thermodynamic-controlled sintering strategy (TCS) has been employed to inhibit the evaporation of metals from ceramic solids. The TCS directly caused the hydrogen permeation flux to reach 1.07 ml·min<sup>−1</sup> cm<sup>−2</sup>, representing a fourfold improvement. Furthermore, F-doping demonstrated enhanced performance at low and medium temperatures. The aforementioned successful strategy provides an effective path for the tailoring of perovskite materials and promotes its application for the industrial-scale separation of hydrogen.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"1 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of a high-performance electrocatalytic acetylene semi-hydrogenation catalyst is the key to the selective removal of acetylene from industrial ethylene gas and non-oil route to ethylene production. However, it is still hampered by the deactivation of the catalyst and hydrogen evolution interference. Here, we proposed an interface engineering strategy involving the Cu and cupric oxide nanoparticles dispersed on amorphous SiO2 (Cu/CuOx/SiO2) by a simple stöber method. x-ray photoelectron spectroscopy demonstrated the strong interfacial interaction between cupric oxide nanoparticles and SiO2. The formed Cu-O-Si interface stabilized the Cuσ+ at high reduction potentials, thus improving the activity and stability of the acetylene reduction reaction, as confirmed by in situ Raman spectroscopy. Consequently, the electrochemical test results showed that at 0.5 M KHCO3, the maximum Faraday efficiency (FE) of ethylene on the optimized Cu/CuOx/SiO2 reached 96%. And ethylene FE remains above 85% at −100 mA cm−2 for 40 h.
研制高性能的电催化乙炔半加氢催化剂是实现工业乙烯气体中乙炔选择性脱除和非油制乙烯的关键。然而，催化剂失活和析氢干扰仍然阻碍了这一过程的进行。在这里，我们提出了一种界面工程策略，通过简单的stöber方法将Cu和氧化铜纳米颗粒分散在无定形SiO2 （Cu/CuOx/SiO2）上。x射线光电子能谱表明，氧化铜纳米颗粒与SiO2之间存在较强的界面相互作用。原位拉曼光谱证实，形成的Cu-O-Si界面使Cuσ+稳定在高还原电位，从而提高了乙炔还原反应的活性和稳定性。因此，电化学测试结果表明，在0.5 M KHCO3条件下，优化后的Cu/CuOx/SiO2上乙烯的最大法拉第效率（FE）达到96%。在−100 mA cm−2条件下，乙烯FE保持在85%以上。
{"title":"Stabilization of cuσ+ via strong Cu-O-Si interface for efficient electrocatalytic acetylene semi-hydrogenation","authors":"Xiaoli Jiang, Wangxin Ge, Yu Fan, Xuedi Sheng, Hongliang Jiang, Chunzhong Li","doi":"10.1002/aic.18663","DOIUrl":"https://doi.org/10.1002/aic.18663","url":null,"abstract":"The development of a high-performance electrocatalytic acetylene semi-hydrogenation catalyst is the key to the selective removal of acetylene from industrial ethylene gas and non-oil route to ethylene production. However, it is still hampered by the deactivation of the catalyst and hydrogen evolution interference. Here, we proposed an interface engineering strategy involving the Cu and cupric oxide nanoparticles dispersed on amorphous SiO<sub>2</sub> (Cu/CuO<sub><i>x</i></sub>/SiO<sub>2</sub>) by a simple stöber method. x-ray photoelectron spectroscopy demonstrated the strong interfacial interaction between cupric oxide nanoparticles and SiO<sub>2</sub>. The formed Cu-O-Si interface stabilized the Cu<sup>σ+</sup> at high reduction potentials, thus improving the activity and stability of the acetylene reduction reaction, as confirmed by in situ Raman spectroscopy. Consequently, the electrochemical test results showed that at 0.5 M KHCO<sub>3</sub>, the maximum Faraday efficiency (FE) of ethylene on the optimized Cu/CuO<sub><i>x</i></sub>/SiO<sub>2</sub> reached 96%. And ethylene FE remains above 85% at −100 mA cm<sup>−2</sup> for 40 h.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"196 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142742796","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Biomass gasification for syngas production is a key operating unit in the biomass utilization process. However, its overall efficiency and stability are often restricted by the presence of complex impurities, including particulate matters (PMs) and tars. In this study, a highly integrated ceramic membrane-based reactor was developed for high-temperature syngas cleaning, enabling the efficient in situ removal of PMs and tars from bio-vapors produced by biomass gasification. Specifically, a silicon carbide (SiC) membrane could separate PMs from biomass volatiles in situ, while a structured Ni15La5/S1-SiC catalyst (nickel and lanthanum-laden silicalite-1 zeolite supported on SiC foam) facilitated the catalytic reforming of tars. Compared to other control reactors (i.e., those containing either a membrane or catalyst alone), the integrated reactor showed synergistic intensification in producing clean syngas from biomass gasification, achieving PM and tar removal efficiencies of up to ~97% and ~90%, and exhibited excellent stability in five-cycle evaluations at 800°C.
{"title":"A highly integrated ceramic membrane-based reactor for intensifying the biomass gasification to clean syngas","authors":"Wei Wei, Qiaoqiao Zhou, Ajing Ding, Shuncheng Li, Feng Zeng, Xuerui Wang, Chong Tian, Zhaoxiang Zhong, Huanhao Chen, Xuehong Gu","doi":"10.1002/aic.18647","DOIUrl":"https://doi.org/10.1002/aic.18647","url":null,"abstract":"Biomass gasification for syngas production is a key operating unit in the biomass utilization process. However, its overall efficiency and stability are often restricted by the presence of complex impurities, including particulate matters (PMs) and tars. In this study, a highly integrated ceramic membrane-based reactor was developed for high-temperature syngas cleaning, enabling the efficient <i>in situ</i> removal of PMs and tars from bio-vapors produced by biomass gasification. Specifically, a silicon carbide (SiC) membrane could separate PMs from biomass volatiles <i>in situ</i>, while a structured Ni<sub>15</sub>La<sub>5</sub>/S1-SiC catalyst (nickel and lanthanum-laden silicalite-1 zeolite supported on SiC foam) facilitated the catalytic reforming of tars. Compared to other control reactors (i.e., those containing either a membrane or catalyst alone), the integrated reactor showed synergistic intensification in producing clean syngas from biomass gasification, achieving PM and tar removal efficiencies of up to ~97% and ~90%, and exhibited excellent stability in five-cycle evaluations at 800°C.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"38 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：