Cu-based electrocatalyst was found to be an efficient catalyst for the formaldehyde oxidation reaction (FOR), capable of generating H2 at the anode. However, their stability is compromised due to unfavorable structural reconstruction during electrolysis. In this work, a pulsed potential electrolysis (PE) strategy was proposed to enhance the stability of a Cu-based electrocatalyst (CuxO@Cu) in FOR. Under constant potential electrolysis (CE), the formic acid (FA) production rate decreased by 77.5 % (22.5 % remained) after the 20 cycles of electrolysis. In contrast, the PE electrolysis mode exhibited excellent stability, and the FA production rate is still 98.9 % of the first cycle. It demonstrated that the PE electrolysis mode induces the continuous oxidation and reduction of the Cu electrocatalyst, leading to reconstruction and then maintenance of the catalyst CuxO/Cu with the optimal Cu0/Cuδ+ ratios, and exposure of advantageous Cu(200) crystal surfaces. Additionally, applying PE could modulate the micro-environment of the electrode by accelerating the mass transfer of the OH– and HCHO. This work provides a new opportunity to achieve a long-term stable electrocatalytic process of Cu electrocatalyst without the complex catalyst modification and design.
{"title":"Pulse potential modulation of Cu-based catalysts for stabilizing formaldehyde oxidation with anodic hydrogen production","authors":"Wei Chen, Yuanqing He, Leitao Xu, Yuqin Zou, Shuangyin Wang, Huan Pang","doi":"10.1016/j.cej.2025.162960","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162960","url":null,"abstract":"Cu-based electrocatalyst was found to be an efficient catalyst for the formaldehyde oxidation reaction (FOR), capable of generating H<sub>2</sub> at the anode. However, their stability is compromised due to unfavorable structural reconstruction during electrolysis. In this work, a pulsed potential electrolysis (PE) strategy was proposed to enhance the stability of a Cu-based electrocatalyst (Cu<sub>x</sub>O@Cu) in FOR. Under constant potential electrolysis (CE), the formic acid (FA) production rate decreased by 77.5 % (22.5 % remained) after the 20 cycles of electrolysis. In contrast, the PE electrolysis mode exhibited excellent stability, and the FA production rate is still 98.9 % of the first cycle. It demonstrated that the PE electrolysis mode induces the continuous oxidation and reduction of the Cu electrocatalyst, leading to reconstruction and then maintenance of the catalyst Cu<sub>x</sub>O/Cu with the optimal Cu<sup>0</sup>/Cu<sup>δ+</sup> ratios, and exposure of advantageous Cu(200) crystal surfaces. Additionally, applying PE could modulate the micro-environment of the electrode by accelerating the mass transfer of the OH<sup>–</sup> and HCHO. This work provides a new opportunity to achieve a long-term stable electrocatalytic process of Cu electrocatalyst without the complex catalyst modification and design.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"7 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.cej.2025.162972
Danbee Park, Hyunwoo Kim, Sangmin Park, Jina Lee, Dong Hun Kwak, Kwang Soo Shin, Yongchan Lee, Hyaekyoung Kim, Jun-Woo Kim, Wangyun Won
Lysine, an essential amino acid, is increasingly used as a feed additive, contributing to increased greenhouse gas emissions from livestock farming. This study aims to comprehensively assess the environmental impact of a newly proposed granule L-lysine (GL) production process in comparison to the conventional powder L-lysine (PL) process using life cycle assessment (LCA). By leveraging operational data from commercial-scale processes, this research provides insights into the potential sustainability benefits of GL production, offering strategic direction for more environmentally friendly lysine manufacturing and feed industry practices. The results revealed global warming potentials of 1.71 kg CO2/kg for PL and 1.00 kg CO2/kg for GL. By coupling LCA with heat integration, this study highlights its role in improving sustainability by reducing heating requirement up to 37 % and 45 % for PL and GL, respectively. Sensitivity analyses showed that optimizing production regions and inputs such as NH3, electricity, steam, and CO2 utilization scenarios significantly enhances environmental performance. Additionally, 18 superstructure-based scenarios provided insights into regional and input-specific impacts. This study highlights the need for environmentally friendly conversion processes and systematic LCA methodologies for L-lysine production. Through a comprehensive LCA, this study identifies a promising production site and an optimal raw material production strategy for a more sustainable feed industry. These findings provide valuable insights for reducing environmental impact and guiding future improvements in lysine manufacturing.Abbreviation: AMS, Ammonium sulfate; BE, Belgium; BMG, Biomass gasification; BFG, Blast furnace gas; BG, Biogas; BR, Brazil; CG, Coal gas; CN, China; CP, Cell protein; CF, Chemical factory; EP, Electrolysis by photovoltaic; EW, Electrolysis by wind turbine; FR, France; FC, Fuel cell; GFLI, Global Feed LCA Institute; GL, Granule L-lysine; GLO, Global; GT, Geothermal; GWP, Global warming potential; HC, Hard coal; HD, Hydro; ISO, International Organization of Standardization; LCA, Life cycle assessment; LCI, Life cycle inventory; LF, Liquid fertilizer; LQ, Liquefaction; MK, Market; MT, Methanol; NC, Nuclear; NG, Natural gas; PL, Powder L-lysine; PV, Photovoltaic; PO, Partial oxidation; RoW, Rest of World; SMR, Steam methane reforming; US, United States; VT, Vent; WC, Wood chips; WD, Wind.
{"title":"Comprehensive life cycle assessment of powder- vs. Granule-form L-lysine production: Evaluating climate impact and sustainability","authors":"Danbee Park, Hyunwoo Kim, Sangmin Park, Jina Lee, Dong Hun Kwak, Kwang Soo Shin, Yongchan Lee, Hyaekyoung Kim, Jun-Woo Kim, Wangyun Won","doi":"10.1016/j.cej.2025.162972","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162972","url":null,"abstract":"Lysine, an essential amino acid, is increasingly used as a feed additive, contributing to increased greenhouse gas emissions from livestock farming. This study aims to comprehensively assess the environmental impact of a newly proposed granule L-lysine (GL) production process in comparison to the conventional powder L-lysine (PL) process using life cycle assessment (LCA). By leveraging operational data from commercial-scale processes, this research provides insights into the potential sustainability benefits of GL production, offering strategic direction for more environmentally friendly lysine manufacturing and feed industry practices. The results revealed global warming potentials of 1.71 kg CO<sub>2</sub>/kg for PL and 1.00 kg CO<sub>2</sub>/kg for GL. By coupling LCA with heat integration, this study highlights its role in improving sustainability by reducing heating requirement up to 37 % and 45 % for PL and GL, respectively. Sensitivity analyses showed that optimizing production regions and inputs such as NH<sub>3</sub>, electricity, steam, and CO<sub>2</sub> utilization scenarios significantly enhances environmental performance. Additionally, 18 superstructure-based scenarios provided insights into regional and input-specific impacts. This study highlights the need for environmentally friendly conversion processes and systematic LCA methodologies for L-lysine production. Through a comprehensive LCA, this study identifies a promising production site and an optimal raw material production strategy for a more sustainable feed industry. These findings provide valuable insights for reducing environmental impact and guiding future improvements in lysine manufacturing.Abbreviation: AMS, Ammonium sulfate; BE, Belgium; BMG, Biomass gasification; BFG, Blast furnace gas; BG, Biogas; BR, Brazil; CG, Coal gas; CN, China; CP, Cell protein; CF, Chemical factory; EP, Electrolysis by photovoltaic; EW, Electrolysis by wind turbine; FR, France; FC, Fuel cell; GFLI, Global Feed LCA Institute; GL, Granule L-lysine; GLO, Global; GT, Geothermal; GWP, Global warming potential; HC, Hard coal; HD, Hydro; ISO, International Organization of Standardization; LCA, Life cycle assessment; LCI, Life cycle inventory; LF, Liquid fertilizer; LQ, Liquefaction; MK, Market; MT, Methanol; NC, Nuclear; NG, Natural gas; PL, Powder L-lysine; PV, Photovoltaic; PO, Partial oxidation; RoW, Rest of World; SMR, Steam methane reforming; US, United States; VT, Vent; WC, Wood chips; WD, Wind.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"13 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.cej.2025.162484
Yoonjung Han, Mine G. Ucak-Astarlioglu, Jedadiah F. Burroughs, Jeffrey W. Bullard
Calcium hydroxide plays a crucial role in various industrial processes. As a primary component of lime mortars, it also facilitates water treatment and supports food processing applications, including pickling and fruit drink fortification. Within portland cement, serves as a key reactant in pozzolanic and carbonation reactions and leaches first from concrete binders when exposed to water. dissolution influences each of these processes. However, limited data exist on how its rate responds to the thermodynamic driving force and temperature changes. This paper presents dissolution rate measurements, using them to determine the apparent activation energy of the rate constant and to identify regimes where different rate-controlling mechanisms dominate. The experiments combine slurries with partially saturated solutions in a vigorously stirred mixed flow reactor that maintains steady-state solution composition. The data reveal a rate equation that explains how surface-controlled dissolution occurs, following chemical kinetic theory. This equation refines numerical cement hydration models involving leaching, carbonation, and pozzolanic reactions.
{"title":"Calcium hydroxide dissolution rates: Dependence on temperature and saturation","authors":"Yoonjung Han, Mine G. Ucak-Astarlioglu, Jedadiah F. Burroughs, Jeffrey W. Bullard","doi":"10.1016/j.cej.2025.162484","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162484","url":null,"abstract":"Calcium hydroxide plays a crucial role in various industrial processes. As a primary component of lime mortars, it also facilitates water treatment and supports food processing applications, including pickling and fruit drink fortification. Within portland cement, <figure><img alt=\"\" height=\"12\" src=\"https://ars.els-cdn.com/content/image/1-s2.0-S1385894725033108-fx1001.jpg\"/></figure> serves as a key reactant in pozzolanic and carbonation reactions and leaches first from concrete binders when exposed to water. <figure><img alt=\"\" height=\"12\" src=\"https://ars.els-cdn.com/content/image/1-s2.0-S1385894725033108-fx1002.jpg\"/></figure> dissolution influences each of these processes. However, limited data exist on how its rate responds to the thermodynamic driving force and temperature changes. This paper presents dissolution rate measurements, using them to determine the apparent activation energy of the rate constant and to identify regimes where different rate-controlling mechanisms dominate. The experiments combine <figure><img alt=\"\" height=\"12\" src=\"https://ars.els-cdn.com/content/image/1-s2.0-S1385894725033108-fx1003.jpg\"/></figure> slurries with partially saturated solutions in a vigorously stirred mixed flow reactor that maintains steady-state solution composition. The data reveal a rate equation that explains how surface-controlled dissolution occurs, following chemical kinetic theory. This equation refines numerical cement hydration models involving leaching, carbonation, and pozzolanic reactions.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"69 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862833","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fire alarm materials played a critical role in the safety of fireman and have gained increasing attention recently. However, the lifetime of traditional reported fire warning materials was short under durable flame attack. Considering explosions and building collapse occurred frequently in fire accidents, developing fire warning sensors with the coupling protection against heat, fire, kinetic impact for advanced flame guarding equipment remained a huge challenge. Here, a multifunctional flame-retardant GO-shear stiffening elastomer (SSE)-EVA sponge (FGSE) featured multiple safeguarding and notable flame tolerance properties was developed by incorporating GO into flame-retardant SSE-EVA composite (FSE). The FSE was prepared by mixing expanded graphite, ammonium polyphosphate with SSE and EVA followed by foaming treatment. Firstly, pure SSE-EVA sponge prepared by foaming SSE and EVA mixture presented low density of 0.41 g/cm3 and 97.8 % shape restoration after 90 %-compressive strain. Importantly, inheriting from the mechanical energy dissipation of SSE, SSE-EVA effectively dissipated impact force from 2625 N to 319 N. Moreover, the limiting oxygen index of FSE with good flame-retardance attained 30 %. Additionally, the incorporation of GO endowed FGSE with temperature sensing characteristics which the resistance rapidly transitioned from insulation to 572 Ω under flaming crashes, and the alarm duration extended to extreme 3600 s. Eventually, an impact-protected flame alarm sensor with multi-channel long-distance system was designed for safety detection in fire rescues.
{"title":"Flame-retardant, lightweight, and multiple safeguarding fire alarm sponge for firefighter safety detection","authors":"Guilin Mei, Sheng Wang, Zimu Li, Wenhui Wang, Zhihao Hu, Yuan Hu, Xinglong Gong","doi":"10.1016/j.cej.2025.162905","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162905","url":null,"abstract":"Fire alarm materials played a critical role in the safety of fireman and have gained increasing attention recently. However, the lifetime of traditional reported fire warning materials was short under durable flame attack. Considering explosions and building collapse occurred frequently in fire accidents, developing fire warning sensors with the coupling protection against heat, fire, kinetic impact for advanced flame guarding equipment remained a huge challenge. Here, a multifunctional flame-retardant GO-shear stiffening elastomer (SSE)-EVA sponge (FGSE) featured multiple safeguarding and notable flame tolerance properties was developed by incorporating GO into flame-retardant SSE-EVA composite (FSE). The FSE was prepared by mixing expanded graphite, ammonium polyphosphate with SSE and EVA followed by foaming treatment. Firstly, pure SSE-EVA sponge prepared by foaming SSE and EVA mixture presented low density of 0.41 g/cm<sup>3</sup> and 97.8 % shape restoration after 90 %-compressive strain. Importantly, inheriting from the mechanical energy dissipation of SSE, SSE-EVA effectively dissipated impact force from 2625 N to 319 N. Moreover, the limiting oxygen index of FSE with good flame-retardance attained 30 %. Additionally, the incorporation of GO endowed FGSE with temperature sensing characteristics which the resistance rapidly transitioned from insulation to 572 Ω under flaming crashes, and the alarm duration extended to extreme 3600 s. Eventually, an impact-protected flame alarm sensor with multi-channel long-distance system was designed for safety detection in fire rescues.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"33 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.cej.2025.162957
Lian Duan, Zhehui Jin
Rarefied gas transports with similar molecular weights (such as CO2 and propane) render similar Knudsen diffusivity in nanochannels. Nevertheless, by using molecular dynamics (MD) simulations, we find that the Knudsen theory breaks down for rarefied CO2 and propane transport in β-cristobalite nanochannels with width of 5 nm under ambient conditions (298 K and 1 atm): CO2 self-diffusivity is only half of that of propane. The drastic differences in their self-diffusivity are due to the penetration of CO2 into the three-dimensional hexagonal ring structures on β-cristobalite surface, resulting in substantial CO2 rotations and curved topological accessible plane, which are detrimental to its diffusion. In contrast, propane cannot penetrate into pore surface. On the other hand, by finely-tuning surface properties (the size of surface Oxygen atoms), we observe drastic-yet-distinct alterations in their self-diffusivities: the enhancement in CO2 self-diffusivities is more than 8-fold of that for propane (290 % v.s. 35 %). This is achieved by prohibiting CO2 penetration and consequently limiting its rotations, thereby largely promoting its transport. On the other hand, the bending structure of propane, coupled with its larger size, always prevents its penetration into regular or tuned (pseudo) surface. Our study indicates that the collective effects of fluid and surface characteristics are instrumental to rarefied gas transport in nanochannels which are largely overlooked in conventional diffusion models and previous experimental as well as simulation studies. This work offers novel insights into rarefied gas transport mechanisms and the development and optimization of advanced materials for gas capture and separation.
{"title":"Drastic-yet-distinct alterations in rarefied gas transport of CO2 and propane in nanochannels by finely-tuning surface characteristics","authors":"Lian Duan, Zhehui Jin","doi":"10.1016/j.cej.2025.162957","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162957","url":null,"abstract":"Rarefied gas transports with similar molecular weights (such as CO<sub>2</sub> and propane) render similar Knudsen diffusivity in nanochannels. Nevertheless, by using molecular dynamics (MD) simulations, we find that the Knudsen theory breaks down for rarefied CO<sub>2</sub> and propane transport in β-cristobalite nanochannels with width of 5 nm under ambient conditions (298 K and 1 atm): CO<sub>2</sub> self-diffusivity is only half of that of propane. The drastic differences in their self-diffusivity are due to the penetration of CO<sub>2</sub> into the three-dimensional hexagonal ring structures on β-cristobalite surface, resulting in substantial CO<sub>2</sub> rotations and curved topological accessible plane, which are detrimental to its diffusion. In contrast, propane cannot penetrate into pore surface. On the other hand, by finely-tuning surface properties (the size of surface Oxygen atoms), we observe drastic-yet-distinct alterations in their self-diffusivities: the enhancement in CO<sub>2</sub> self-diffusivities is more than 8-fold of that for propane (290 % v.s. 35 %). This is achieved by prohibiting CO<sub>2</sub> penetration and consequently limiting its rotations, thereby largely promoting its transport. On the other hand, the bending structure of propane, coupled with its larger size, always prevents its penetration into regular or tuned (pseudo) surface. Our study indicates that the collective effects of fluid and surface characteristics are instrumental to rarefied gas transport in nanochannels which are largely overlooked in conventional diffusion models and previous experimental as well as simulation studies. This work offers novel insights into rarefied gas transport mechanisms and the development and optimization of advanced materials for gas capture and separation.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"13 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Discharge plasma presents a promising approach for converting heavy oil into light hydrocarbons under room temperature and atmospheric pressure. Among various techniques, repetitive pulsed discharge plasma is preferred for its potential to improve energy efficiency, however the decomposition characteristics and gaseous production pathways of long-chain hydrocarbons remain insufficiently understood. In this study, the decomposed products and process of mineral transformer oil under repetitively pulsed spark discharge in the liquid phase are analyzed by gas chromatography (GC) and optical emission spectroscopy (OES). Experiment results revealed that the proportion of H2 gas production decreases, while that of C2H2 increases with the prolonged reaction time. Besides, the production of C2H2 is significantly higher at a pulse frequency of 1000 Hz compared to 10 Hz. OES analysis further shows that the electron density decreases as the repetitive pulse frequency increases, a trend that contrasts with prior observations of heavy oil cracking in gas and liquid–gas reaction systems. Despite the reduced energy per pulse at higher frequencies, the total number of breakdown events over the same reaction duration is larger, contributing to enhanced reaction outcomes. These experimental findings are confirmed by plasma kinetics and molecular dynamics simulation, which identified a continuous dehydrogenation process involving H radical reactions with C2H4 as the primary pathway for C2H2 and H2 production. The study demonstrates the feasibility of C2-oriented conversion through the decomposition of heavy oil decomposition under spark discharge, with adjustments to repetitive pulse parameters offering a promising avenue for optimization.
{"title":"Oriented conversion of low-value heavy oil to acetylene and hydrogen using pulsed spark discharge","authors":"Hang Wang, Rui Wu, Liguang Dou, Dengke Xi, Bangdou Huang, Zhuofei Wang, Shuai Zhang, Zhe Fan, Shuai Yang, Cheng Zhang, Guoxing Chen, Tao Shao","doi":"10.1016/j.cej.2025.162956","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162956","url":null,"abstract":"Discharge plasma presents a promising approach for converting heavy oil into light hydrocarbons under room temperature and atmospheric pressure. Among various techniques, repetitive pulsed discharge plasma is preferred for its potential to improve energy efficiency, however the decomposition characteristics and gaseous production pathways of long-chain hydrocarbons remain insufficiently understood. In this study, the decomposed products and process of mineral transformer oil under repetitively pulsed spark discharge in the liquid phase are analyzed by gas chromatography (GC) and optical emission spectroscopy (OES). Experiment results revealed that the proportion of H<sub>2</sub> gas production decreases, while that of C<sub>2</sub>H<sub>2</sub> increases with the prolonged reaction time. Besides, the production of C<sub>2</sub>H<sub>2</sub> is significantly higher at a pulse frequency of 1000 Hz compared to 10 Hz. OES analysis further shows that the electron density decreases as the repetitive pulse frequency increases, a trend that contrasts with prior observations of heavy oil cracking in gas and liquid–gas reaction systems. Despite the reduced energy per pulse at higher frequencies, the total number of breakdown events over the same reaction duration is larger, contributing to enhanced reaction outcomes. These experimental findings are confirmed by plasma kinetics and molecular dynamics simulation, which identified a continuous dehydrogenation process involving H radical reactions with C<sub>2</sub>H<sub>4</sub> as the primary pathway for C<sub>2</sub>H<sub>2</sub> and H<sub>2</sub> production. The study demonstrates the feasibility of C<sub>2</sub>-oriented conversion through the decomposition of heavy oil decomposition under spark discharge, with adjustments to repetitive pulse parameters offering a promising avenue for optimization.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"128 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.cej.2025.162976
Longjian Li, Ping Zhang, Reyila Tuerhong, Yongchong Yu, Keyi Chai, Lianbiao Zhao, Xiaoping Su, Lijuan Han
Enabling the oxidation of ammonia (NH3), a product of nitrogen (N2) reduction, to nitric acid (HNO3) can boost the economic value of overall N2 photofixation. In this work, we constructed a Cu doped NiO@C nanosheets photocatalyst with dipole polarization effect, achieving efficient overall N2 photofixation (N2 → NH3 → HNO3) with a relatively high proportion of NO3− (92.3 %). Mechanistic studies reveal that the band structure modulation of photocatalyst and thus enhanced the oxidation capacity, further significantly promoted the NH3 → HNO3 pathway and increased the proportion of NO3− in the overall N2 photofixation products. The local polarization brought along the Cu-Ni atomic interface, which promoted photo-excited charge transfer process, enhanced N2 absorption/activation capability and promoted the N2 → NH3 pathway. First-principles density functional theory (DFT) calculations demonstrate that the Cu doping strategy reduce the N2 reduction reaction (NRR) energy barrier. This work provides an approach for optimizing the overall N2 photofixation through band structure modulation and dipole polarization effect.
{"title":"Dipole-polarized Cu–Ni atomic interfaces for synergistic enhancement and steering of overall nitrogen photofixation","authors":"Longjian Li, Ping Zhang, Reyila Tuerhong, Yongchong Yu, Keyi Chai, Lianbiao Zhao, Xiaoping Su, Lijuan Han","doi":"10.1016/j.cej.2025.162976","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162976","url":null,"abstract":"Enabling the oxidation of ammonia (NH<sub>3</sub>), a product of nitrogen (N<sub>2</sub>) reduction, to nitric acid (HNO<sub>3</sub>) can boost the economic value of overall N<sub>2</sub> photofixation. In this work, we constructed a Cu doped NiO@C nanosheets photocatalyst with dipole polarization effect, achieving efficient overall N<sub>2</sub> photofixation (N<sub>2</sub> → NH<sub>3</sub> → HNO<sub>3</sub>) with a relatively high proportion of NO<sub>3</sub><sup>−</sup> (92.3 %). Mechanistic studies reveal that the band structure modulation of photocatalyst and thus enhanced the oxidation capacity, further significantly promoted the NH<sub>3</sub> → HNO<sub>3</sub> pathway and increased the proportion of NO<sub>3</sub><sup>−</sup> in the overall N<sub>2</sub> photofixation products. The local polarization brought along the Cu-Ni atomic interface, which promoted photo-excited charge transfer process, enhanced N<sub>2</sub> absorption/activation capability and promoted the N<sub>2</sub> → NH<sub>3</sub> pathway. First-principles density functional theory (DFT) calculations demonstrate that the Cu doping strategy reduce the N<sub>2</sub> reduction reaction (NRR) energy barrier. This work provides an approach for optimizing the overall N<sub>2</sub> photofixation through band structure modulation and dipole polarization effect.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"63 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862832","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.cej.2025.162786
Yue Li, Kang Xu, Weijiang Hu, Ziling Huang, Qing Li, Liang Cao, Minjie Shi, Zhefei Wang, Huaixin Wei, Jun Yang
To ensure even distribution of sodium ions in sodium-metal batteries, various components must be incorporated to strengthen the surface mechanically, suppress dendritic growth, and create an ideal solid electrolyte interphase (SEI) characterized by robust adhesion, superior electrical conductivity, and exceptional mechanical durability. A novel bifunctional artificial interfacial protective layer was first designed by in-situ deposition and reconfiguration of vanadium fluoride on the surface of sodium metal. This reaction produced two components, V and NaF, in a spontaneous manner. It has been demonstrated that NaF offers excellent ionic conductivity and electronic insulation, facilitating the rapid adsorption of Na+ onto the electrode surface without reduction. In contrast, vanadium exhibits exceptional sodiophilicity, effectively regulating the uniform deposition of sodium ions to promote a stable deposition-stripping cycle. Additionally, the multiphase interfacial layer comprising NaF/V offers both chemical and electrochemical stability, along with a notably high Young’s modulus of 17.7 GPa, thus ensuring the long-term stability and safety of the device. Sodium metal anodes as inhibitors of dendrite growth, the VFx/Na demonstrates prolonged cycling stability of up to 1000 h at 0.5 mA cm−2 and 1 mAh cm−2 in symmetric cell. In the electrochemical test of a full battery with a Na3V2(PO4)3 cathode, the VFx/Na electrode showed superior performance, maintaining a specific capacity of 76.3 mAh g−1 at a current density of 5 A g−1 for a stable cycle of 4000 turns.
{"title":"In situ reconstructed dual-functional interfacial layer induced by spontaneous vanadium fluoride reaction for highly stable sodium metal batteries","authors":"Yue Li, Kang Xu, Weijiang Hu, Ziling Huang, Qing Li, Liang Cao, Minjie Shi, Zhefei Wang, Huaixin Wei, Jun Yang","doi":"10.1016/j.cej.2025.162786","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162786","url":null,"abstract":"To ensure even distribution of sodium ions in sodium-metal batteries, various components must be incorporated to strengthen the surface mechanically, suppress dendritic growth, and create an ideal solid electrolyte interphase (SEI) characterized by robust adhesion, superior electrical conductivity, and exceptional mechanical durability. A novel bifunctional artificial interfacial protective layer was first designed by in-situ deposition and reconfiguration of vanadium fluoride on the surface of sodium metal. This reaction produced two components, V and NaF, in a spontaneous manner. It has been demonstrated that NaF offers excellent ionic conductivity and electronic insulation, facilitating the rapid adsorption of Na<sup>+</sup> onto the electrode surface without reduction. In contrast, vanadium exhibits exceptional sodiophilicity, effectively regulating the uniform deposition of sodium ions to promote a stable deposition-stripping cycle. Additionally, the multiphase interfacial layer comprising NaF/V offers both chemical and electrochemical stability, along with a notably high Young’s modulus of 17.7 GPa, thus ensuring the long-term stability and safety of the device. Sodium metal anodes as inhibitors of dendrite growth, the VF<sub>x</sub>/Na demonstrates prolonged cycling stability of up to 1000 h at 0.5 mA cm<sup>−2</sup> and 1 mAh cm<sup>−2</sup> in symmetric cell. In the electrochemical test of a full battery with a Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> cathode, the VF<sub>x</sub>/Na electrode showed superior performance, maintaining a specific capacity of 76.3 mAh g<sup>−1</sup> at a current density of 5 A g<sup>−1</sup> for a stable cycle of 4000 turns.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"131 3 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Graphene-based nanomaterials (GBNMs), which are tiny carbon-based materials with exceptional electrical and mechanical properties, have a wide range of applications in biological research due to their unique characteristics, including their elevated conductivity, substantial surface area, and adjustable fluorescence. However, the understanding of how GI microbiota affects such basic processes in GBNMs is far from complete. Hence, the current review is expected to highlight the revolutionary potential that graphene quantum dots (GQDs) and other GBNMs have in surging microbiome research; this includes their role in addressing critical challenges concerning precision medicine and applications in identifying microbial metabolites. GBNMs facilitate the accurate identification of essential metabolites in the gastrointestinal (GI) microbiome, including short-chain fatty acids (SCFAs) and indoles, offering insights into the intricate relationships between microbiome composition and GI disorders such as inflammatory bowel disease (IBD) and irritable bowel syndrome (IBS). Additionally, GBNMs play a crucial role in understanding antibiotic resistance by enabling the development of advanced biosensors that can rapidly detect bacterial pathogens, track resistance mechanisms, and monitor the effectiveness of antibiotics, thus providing valuable insights into the dynamics of resistance and aiding in the development of targeted therapeutic strategies. Moreover, GBNMs’ sensitivity and specificity are essential in creating tailored diagnostic platforms, enhancing precision medicine applications. This review highlights current accomplishments and outlines future research paths, emphasizing the revolutionary impact of GBNMs in microbiome research and personalized healthcare.
{"title":"Advancing gut microbiome insights: Graphene quantum dot nanobiosensors for microbial metabolite detection","authors":"Soheil Sadr, Shakiba Nazemian, Shiva Dianaty, Ashkan Hajjafari, Bita Fazel, Arezou Rezaei, Abbas Rahdar, Sonia Fathi-Karkan, Mansour Bayat, Sadanand Pandey, Octavio Luiz Franco, Luiz Fernando Romanholo Ferreira, Zelal Kharaba, Hassan Borji","doi":"10.1016/j.cej.2025.162954","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162954","url":null,"abstract":"Graphene-based nanomaterials (GBNMs), which are tiny carbon-based materials with exceptional electrical and mechanical properties, have a wide range of applications in biological research due to their unique characteristics, including their elevated conductivity, substantial surface area, and adjustable fluorescence. However, the understanding of how GI microbiota affects such basic processes in GBNMs is far from complete. Hence, the current review is expected to highlight the revolutionary potential that graphene quantum dots (GQDs) and other GBNMs have in surging microbiome research; this includes their role in addressing critical challenges concerning precision medicine and applications in identifying microbial metabolites. GBNMs facilitate the accurate identification of essential metabolites in the gastrointestinal (GI) microbiome, including short-chain fatty acids (SCFAs) and indoles, offering insights into the intricate relationships between microbiome composition and GI disorders such as inflammatory bowel disease (IBD) and irritable bowel syndrome (IBS). Additionally, GBNMs play a crucial role in understanding antibiotic resistance by enabling the development of advanced biosensors that can rapidly detect bacterial pathogens, track resistance mechanisms, and monitor the effectiveness of antibiotics, thus providing valuable insights into the dynamics of resistance and aiding in the development of targeted therapeutic strategies. Moreover, GBNMs’ sensitivity and specificity are essential in creating tailored diagnostic platforms, enhancing precision medicine applications. This review highlights current accomplishments and outlines future research paths, emphasizing the revolutionary impact of GBNMs in microbiome research and personalized healthcare.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"13 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.cej.2025.162965
Denny Gunawan, Tahlia Stern, Jiajun Zhang, Jodie A. Yuwono, Jian Pan, Qiyuan Li, Haolin Yu, Michael Gunawan, Rosalie K. Hocking, Cui Ying Toe, Jason Scott, Rose Amal
Organic photoreforming represents a promising pathway for solar H2 generation with the coproduction of valuable byproducts. However, its development has been limited by separate studies on photocatalysts or photoreactors, with little focus on cost and scalability. Here we integrate photocatalyst design, upscaled photoreactor engineering, and cost analysis for the solar-driven reforming of alcohol feedstock to H2. The process was optimized by examining various alcohol compounds and Ni cocatalyst impact on Zn3In2S6 photocatalytic activity. Strong interactions between Zn3In2S6 and both aromatic benzyl alcohol substrate and Ni intensified H2 evolution and benzaldehyde formation, achieving an apparent quantum yield of 63.8 % at 420 nm and an areal H2 evolution activity of 278 mmol h−1 m−2 under simulated sunlight. Using the optimum conditions established in a laboratory environment, an upscaled slurry photoreactor prototype was designed and operated under natural sunlight with a 0.5 m2 light receiving area. The upscaled solar-driven reforming of benzyl alcohol over Ni/Zn3In2S6 delivered a H2 production rate of 1.67 normal L h−1, corresponding to an areal H2 evolution activity of 139 mmol h−1 m−2, with benzaldehyde as the major organic byproduct. A pathway for commercially viable large-scale solar-driven organic reforming was defined through techno-economic assessment. The findings are a crucial advancement in scaling photoreforming towards commercialization.
{"title":"Scalable solar-driven reforming of alcohol feedstock to H2 using Ni/Zn3In2S6 photocatalyst","authors":"Denny Gunawan, Tahlia Stern, Jiajun Zhang, Jodie A. Yuwono, Jian Pan, Qiyuan Li, Haolin Yu, Michael Gunawan, Rosalie K. Hocking, Cui Ying Toe, Jason Scott, Rose Amal","doi":"10.1016/j.cej.2025.162965","DOIUrl":"https://doi.org/10.1016/j.cej.2025.162965","url":null,"abstract":"Organic photoreforming represents a promising pathway for solar H<sub>2</sub> generation with the coproduction of valuable byproducts. However, its development has been limited by separate studies on photocatalysts or photoreactors, with little focus on cost and scalability. Here we integrate photocatalyst design, upscaled photoreactor engineering, and cost analysis for the solar-driven reforming of alcohol feedstock to H<sub>2</sub>. The process was optimized by examining various alcohol compounds and Ni cocatalyst impact on Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub> photocatalytic activity. Strong interactions between Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub> and both aromatic benzyl alcohol substrate and Ni intensified H<sub>2</sub> evolution and benzaldehyde formation, achieving an apparent quantum yield of 63.8 % at 420 nm and an areal H<sub>2</sub> evolution activity of 278 mmol h<sup>−1</sup> m<sup>−2</sup> under simulated sunlight. Using the optimum conditions established in a laboratory environment, an upscaled slurry photoreactor prototype was designed and operated under natural sunlight with a 0.5 m<sup>2</sup> light receiving area. The upscaled solar-driven reforming of benzyl alcohol over Ni/Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub> delivered a H<sub>2</sub> production rate of 1.67 normal L h<sup>−1</sup>, corresponding to an areal H<sub>2</sub> evolution activity of 139 mmol h<sup>−1</sup> m<sup>−2</sup>, with benzaldehyde as the major organic byproduct. A pathway for commercially viable large-scale solar-driven organic reforming was defined through techno-economic assessment. The findings are a crucial advancement in scaling photoreforming towards commercialization.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"40 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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