Pub Date : 2025-01-03DOI: 10.1021/acssuschemeng.4c07186
Yunhe Zhang, Yun Huang, Changjian Zhang, Yang Gao, Yanzhou Wang, Caixia Li, Yiheng Wang, Xing Li, Mingshan Wang, Yuanhua Lin
Aqueous zinc-ion batteries (AZIBs) have gained increasing attention for grid energy storage systems. However, ensuring the long-term reversible operation of the zinc anode remains a challenge due to dendrite growth and adverse side reactions during the charge and discharge cycles. This study investigates the use of d-pantothenic acid (D-PA) as an additive in 2 M ZnSO4 aqueous electrolyte to enhance the cycling stability of the zinc anode in AZIBs. Experimental results and theoretical calculations demonstrate that D-PA reshapes the solvation structure of Zn2+ by partially replacing coordinated water molecules, ensuring the stability of Zn2+ transport. Furthermore, D-PA adsorbs on active sites of the zinc anode, increasing the surface overpotential (|ηs|), reducing the nucleation energy barrier, and decreasing the critical nucleus size (rcrit), thus ensuring uniform zinc deposition. This dual role of modifying the Zn2+ solvation shell and regulating Zn2+ nucleation effectively mitigates dendrite growth and suppresses side reactions, resulting in excellent stability of the zinc anode. Consequently, Zn||Zn symmetrical cells with the D-PA additive maintain stable operation for over 2000 h at 1.0 mA cm–2 and 1.0 mA h cm–2, and nearly 4000 h at 4.0 mA cm–2 and 4.0 mA h cm–2. Additionally, Zn||Cu asymmetric cells exhibit cycling stability over 300 cycles at 0.5 mA cm–2 and 0.5 mA h cm–2, with an average Coulombic efficiency of 99.29%. Moreover, Zn||V2O5 full cells containing the D-PA additive exhibit stable cycling performance over 1000 cycles at a current density of 1 A g–1, maintaining a high capacity retention. Specifically, the initial capacity of the full cell is around 161.17 mA h g–1, with approximately 62.7% capacity retention after 1000 cycles.
{"title":"Synergistic Solvation and Nucleation Regulation for Enhanced Stability and Longevity in Aqueous Zinc-Ion Batteries with d-Pantothenic Acid Additive","authors":"Yunhe Zhang, Yun Huang, Changjian Zhang, Yang Gao, Yanzhou Wang, Caixia Li, Yiheng Wang, Xing Li, Mingshan Wang, Yuanhua Lin","doi":"10.1021/acssuschemeng.4c07186","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07186","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) have gained increasing attention for grid energy storage systems. However, ensuring the long-term reversible operation of the zinc anode remains a challenge due to dendrite growth and adverse side reactions during the charge and discharge cycles. This study investigates the use of <span>d</span>-pantothenic acid (D-PA) as an additive in 2 M ZnSO<sub>4</sub> aqueous electrolyte to enhance the cycling stability of the zinc anode in AZIBs. Experimental results and theoretical calculations demonstrate that D-PA reshapes the solvation structure of Zn<sup>2+</sup> by partially replacing coordinated water molecules, ensuring the stability of Zn<sup>2+</sup> transport. Furthermore, D-PA adsorbs on active sites of the zinc anode, increasing the surface overpotential (|η<sub>s</sub>|), reducing the nucleation energy barrier, and decreasing the critical nucleus size (<i>r</i><sub>crit</sub>), thus ensuring uniform zinc deposition. This dual role of modifying the Zn<sup>2+</sup> solvation shell and regulating Zn<sup>2+</sup> nucleation effectively mitigates dendrite growth and suppresses side reactions, resulting in excellent stability of the zinc anode. Consequently, Zn||Zn symmetrical cells with the D-PA additive maintain stable operation for over 2000 h at 1.0 mA cm<sup>–2</sup> and 1.0 mA h cm<sup>–2</sup>, and nearly 4000 h at 4.0 mA cm<sup>–2</sup> and 4.0 mA h cm<sup>–2</sup>. Additionally, Zn||Cu asymmetric cells exhibit cycling stability over 300 cycles at 0.5 mA cm<sup>–2</sup> and 0.5 mA h cm<sup>–2</sup>, with an average Coulombic efficiency of 99.29%. Moreover, Zn||V<sub>2</sub>O<sub>5</sub> full cells containing the D-PA additive exhibit stable cycling performance over 1000 cycles at a current density of 1 A g<sup>–1</sup>, maintaining a high capacity retention. Specifically, the initial capacity of the full cell is around 161.17 mA h g<sup>–1</sup>, with approximately 62.7% capacity retention after 1000 cycles.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-03DOI: 10.1021/acssuschemeng.4c05352
Min Ying Liow, Eng-Seng Chan, Wei Zhe Ng, Cher Pin Song
Enzymatic biodiesel production often faces challenges such as mass transfer limitations and enzyme sensitivity, resulting in low reaction efficiency. This study aimed to address these issues by integrating ultrasound technology with low-cost CO2-based alkyl carbamate ionic liquids (ILs) as additives. Among the investigated carbamate ILs, N,N-diallylammonium N′,N′-diallylcarbamate (DACARB) demonstrated the highest fatty acid methyl ester (FAME) content in ultrasound-assisted biodiesel production catalyzed by Eversa Transform 2.0 at an optimal temperature of 50 °C. The addition of DACARB improved the solubility of immiscible reactants and enhanced lipase stability, maintaining high FAME yields even under ultrasound amplitudes of up to 100% and duty cycles of 20%. Enzyme hydrolytic activity assays revealed that DACARB activated the lipase, increasing enzyme activity by 33% through favorable alterations in the enzyme tertiary structure, as confirmed by fluorescence spectroscopy. Furthermore, employing a stepwise methanol dosing strategy with ultrasound at 40% amplitude and 5% duty cycle in the presence of 2 wt % DACARB achieved a FAME content of 91.3 wt % within 12 h, using only 0.2 wt % enzyme concentration. This study highlights the potential of DACARB as a promising additive to enhance the efficiency of ultrasound-assisted enzymatic biodiesel production, offering a promising solution to overcome current limitations in the process.
{"title":"Enhancing Enzymatic Biodiesel Production Using Low-Cost CO2-Based Alkyl Carbamate Ionic Liquid and Ultrasound-Assisted Intensification","authors":"Min Ying Liow, Eng-Seng Chan, Wei Zhe Ng, Cher Pin Song","doi":"10.1021/acssuschemeng.4c05352","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05352","url":null,"abstract":"Enzymatic biodiesel production often faces challenges such as mass transfer limitations and enzyme sensitivity, resulting in low reaction efficiency. This study aimed to address these issues by integrating ultrasound technology with low-cost CO<sub>2</sub>-based alkyl carbamate ionic liquids (ILs) as additives. Among the investigated carbamate ILs, <i>N</i>,<i>N</i>-diallylammonium <i>N</i>′,<i>N</i>′-diallylcarbamate (DACARB) demonstrated the highest fatty acid methyl ester (FAME) content in ultrasound-assisted biodiesel production catalyzed by Eversa Transform 2.0 at an optimal temperature of 50 °C. The addition of DACARB improved the solubility of immiscible reactants and enhanced lipase stability, maintaining high FAME yields even under ultrasound amplitudes of up to 100% and duty cycles of 20%. Enzyme hydrolytic activity assays revealed that DACARB activated the lipase, increasing enzyme activity by 33% through favorable alterations in the enzyme tertiary structure, as confirmed by fluorescence spectroscopy. Furthermore, employing a stepwise methanol dosing strategy with ultrasound at 40% amplitude and 5% duty cycle in the presence of 2 wt % DACARB achieved a FAME content of 91.3 wt % within 12 h, using only 0.2 wt % enzyme concentration. This study highlights the potential of DACARB as a promising additive to enhance the efficiency of ultrasound-assisted enzymatic biodiesel production, offering a promising solution to overcome current limitations in the process.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"72 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sustainable batteries using nontoxic, earth-abundant, and low-cost materials are key to decarbonization. Olivine NaFePO4 fulfills these criteria, is attractive for Na-ion batteries, and can be derived from LiFePO4 recycled from Li-ion battery wastes. Critical knowledge is needed for transforming LiFePO4 to NaFePO4 to enable such a sustainable, green engineering path toward high-performance Na-ion batteries. Herein, we report on the development of a stable-cycling, sustainable olivine iron phosphate-based Na-ion battery empowered by an improved understanding of materials transformation and electrolyte chemistry. First, we found that the conventional carbonate electrolyte with fluoroethylene carbonate additive causes an additional plateau (∼2.4 V) at the end of the discharge process of the FePO4||Na metal cell, leading to lower initial discharge capacity and voltage. This result shows that the voltage profile is influenced by not only intrinsic materials phase transformation during battery cycling but also the electrolyte additives and interphases formed. With the 1 M NaPF6 diglyme electrolyte, we achieved an excellent capacity retention of 96% and 98% after 500 cycles at 1 and 5 C, respectively. Second, we chemically sodiated FePO4 to form single-phase Na0.9FePO4. Na0.9FePO4||hard carbon full cells demonstrated a remarkable capacity retention of ∼84% at 3 and 5 C after 1000 cycles. The successful implementation of hard carbon, which can be derived from biomass waste, will further improve the sustainability of energy storage technologies. Our research demonstrates that electrolyte chemistry influences the voltage profile of phase-changing electrodes and provides effective electrolyte and full-cell design solutions for stable-cycling NaFePO4.
{"title":"Stable-Cycling Sustainable Na-Ion Batteries with Olivine Iron Phosphate Cathode in an Ether Electrolyte","authors":"Dawei Xia, Weibo Huang, Chenguang Shi, Anika Promi, Dong Hou, Chengjun Sun, Sooyeon Hwang, Gihan Kwon, Haibo Huang, Feng Lin","doi":"10.1021/acssuschemeng.4c06900","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06900","url":null,"abstract":"Sustainable batteries using nontoxic, earth-abundant, and low-cost materials are key to decarbonization. Olivine NaFePO<sub>4</sub> fulfills these criteria, is attractive for Na-ion batteries, and can be derived from LiFePO<sub>4</sub> recycled from Li-ion battery wastes. Critical knowledge is needed for transforming LiFePO<sub>4</sub> to NaFePO<sub>4</sub> to enable such a sustainable, green engineering path toward high-performance Na-ion batteries. Herein, we report on the development of a stable-cycling, sustainable olivine iron phosphate-based Na-ion battery empowered by an improved understanding of materials transformation and electrolyte chemistry. First, we found that the conventional carbonate electrolyte with fluoroethylene carbonate additive causes an additional plateau (∼2.4 V) at the end of the discharge process of the FePO<sub>4</sub>||Na metal cell, leading to lower initial discharge capacity and voltage. This result shows that the voltage profile is influenced by not only intrinsic materials phase transformation during battery cycling but also the electrolyte additives and interphases formed. With the 1 M NaPF<sub>6</sub> diglyme electrolyte, we achieved an excellent capacity retention of 96% and 98% after 500 cycles at 1 and 5 C, respectively. Second, we chemically sodiated FePO<sub>4</sub> to form single-phase Na<sub>0.9</sub>FePO<sub>4</sub>. Na<sub>0.9</sub>FePO<sub>4</sub>||hard carbon full cells demonstrated a remarkable capacity retention of ∼84% at 3 and 5 C after 1000 cycles. The successful implementation of hard carbon, which can be derived from biomass waste, will further improve the sustainability of energy storage technologies. Our research demonstrates that electrolyte chemistry influences the voltage profile of phase-changing electrodes and provides effective electrolyte and full-cell design solutions for stable-cycling NaFePO<sub>4</sub>.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917121","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
During CO2/HCO3– reduction with renewable biomass, achieving high-efficiency production of the target products is vital but challenging. In this study, an NH2– functional-group-modified MIL-53(Fe) catalyst was synthesized using a facile and efficient method. Under the action of the NH2-MIL-53(Fe) catalyst, a clear synergistic effect was exhibited on the transformation of glucose and NaHCO3 into formic acid with a high yield of 50% at a low reaction temperature (190 °C) via a three-pronged route, which mainly involved the decomposition of intermediates of glucose to gradually reduce NaHCO3 to formic acid under hydrothermal conditions. An in-depth analysis of the catalytic mechanism and density functional theory calculations demonstrated that the increased alkalinity of active sites by the NH2– functional group incorporation into the catalytic system enhanced the crucial reaction steps and reduced the activation energy of the crucial reactions, including glucose isomerization, aldehyde intermediate retro-aldol condensation, and redox of aldehyde compounds and NaHCO3 to formic acid, thereby promoting the generation of target products and suppressing side products. This study addresses the challenge of reducing NaHCO3 from renewable biomass to commercial formic acid by constructing multifunctional active sites, thus providing a new strategy for achieving carbon cycling.
{"title":"Synergistic Hydrothermal Conversion of Biomass Derivative Carbohydrates and CO2 into Value-Added Organic Acid over an NH2-MIL-53(Fe) Catalyst","authors":"Meng Xia, Longqi Li, Xiaocong Wang, Kaihao Xu, Shuai Zhang, Chengxue Zhang","doi":"10.1021/acssuschemeng.4c07721","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07721","url":null,"abstract":"During CO<sub>2</sub>/HCO<sub>3</sub><sup>–</sup> reduction with renewable biomass, achieving high-efficiency production of the target products is vital but challenging. In this study, an NH<sub>2</sub>– functional-group-modified MIL-53(Fe) catalyst was synthesized using a facile and efficient method. Under the action of the NH<sub>2</sub>-MIL-53(Fe) catalyst, a clear synergistic effect was exhibited on the transformation of glucose and NaHCO<sub>3</sub> into formic acid with a high yield of 50% at a low reaction temperature (190 °C) via a three-pronged route, which mainly involved the decomposition of intermediates of glucose to gradually reduce NaHCO<sub>3</sub> to formic acid under hydrothermal conditions. An in-depth analysis of the catalytic mechanism and density functional theory calculations demonstrated that the increased alkalinity of active sites by the NH<sub>2</sub>– functional group incorporation into the catalytic system enhanced the crucial reaction steps and reduced the activation energy of the crucial reactions, including glucose isomerization, aldehyde intermediate retro-aldol condensation, and redox of aldehyde compounds and NaHCO<sub>3</sub> to formic acid, thereby promoting the generation of target products and suppressing side products. This study addresses the challenge of reducing NaHCO<sub>3</sub> from renewable biomass to commercial formic acid by constructing multifunctional active sites, thus providing a new strategy for achieving carbon cycling.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"35 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917122","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-03DOI: 10.1021/acssuschemeng.4c08836
Patrycja Taborowska, Anna Mielańczyk, Andrzej Dzienia, Dawid Janas
Single-walled carbon nanotubes (SWCNTs) are promising materials for electronics and photonics due to their unique properties. To achieve high performance, the sorting of as-synthesized SWCNT mixtures is necessary, generating material with defined properties tailored for a specific application. Currently, it is possible to obtain such materials by using several SWCNT partitioning methods. However, such procedures require further improvements to unlock the industrial-scale production of SWCNTs of properties tailored for a specific application. The overall low efficiency of the SWCNT purification process and its nonsustainable nature are among the numerous obstacles that hinder their potential applications. Herein, we employed multiple rounds of conjugated polymer extraction (CPE) with a novel conjugated polymer (CP) addition scheme to considerably increase the amounts of isolated (6,5) and (7,5) SWCNTs, reaching up to 25% and 10%, respectively. While maintaining high chiral purity, the consumption of SWCNT raw material and CP was substantially reduced. This translated to a reduction of costs for the isolation of 1 mg of monochiral SWCNTs by nearly half compared with the most efficient chromatographic methods to date. Besides that, the proposed strategy, which relied on the deliberate addition of 4 times weight excess of the polymer with respect to SWCNTs at the initial extraction step, facilitated very short processing (sonication and centrifugation), shortening the purification time by ca. 76%, compared to the high volume shear-mixing technique, while simultaneously reducing electricity consumption. A series of consecutive isolations required only a modest addition of polymer to reach the desired SWCNT separation yield. Such a stepwise approach displayed considerable benefits compared to a typically engaged single-stage CPE process, achieving an unprecedented extraction performance. Most importantly, we show that the proposed approach fulfills the principles of green chemistry. First, the raw material consumption is reduced through repeated use or recycling, further enhancing the sustainability and cost-effectiveness of recurrent chirality-selective isolation of SWCNTs. Second, we discovered that the process may be conducted in naturally occurring green solvents such as p-cymene, thus avoiding the typically employed hazardous organic liquid media.
{"title":"Environmentally Conscious Highly Effective Sorting of Single-Walled Carbon Nanotubes Using Recurrent Conjugated Polymer Extraction","authors":"Patrycja Taborowska, Anna Mielańczyk, Andrzej Dzienia, Dawid Janas","doi":"10.1021/acssuschemeng.4c08836","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08836","url":null,"abstract":"Single-walled carbon nanotubes (SWCNTs) are promising materials for electronics and photonics due to their unique properties. To achieve high performance, the sorting of as-synthesized SWCNT mixtures is necessary, generating material with defined properties tailored for a specific application. Currently, it is possible to obtain such materials by using several SWCNT partitioning methods. However, such procedures require further improvements to unlock the industrial-scale production of SWCNTs of properties tailored for a specific application. The overall low efficiency of the SWCNT purification process and its nonsustainable nature are among the numerous obstacles that hinder their potential applications. Herein, we employed multiple rounds of conjugated polymer extraction (CPE) with a novel conjugated polymer (CP) addition scheme to considerably increase the amounts of isolated (6,5) and (7,5) SWCNTs, reaching up to 25% and 10%, respectively. While maintaining high chiral purity, the consumption of SWCNT raw material and CP was substantially reduced. This translated to a reduction of costs for the isolation of 1 mg of monochiral SWCNTs by nearly half compared with the most efficient chromatographic methods to date. Besides that, the proposed strategy, which relied on the deliberate addition of 4 times weight excess of the polymer with respect to SWCNTs at the initial extraction step, facilitated very short processing (sonication and centrifugation), shortening the purification time by ca. 76%, compared to the high volume shear-mixing technique, while simultaneously reducing electricity consumption. A series of consecutive isolations required only a modest addition of polymer to reach the desired SWCNT separation yield. Such a stepwise approach displayed considerable benefits compared to a typically engaged single-stage CPE process, achieving an unprecedented extraction performance. Most importantly, we show that the proposed approach fulfills the principles of green chemistry. First, the raw material consumption is reduced through repeated use or recycling, further enhancing the sustainability and cost-effectiveness of recurrent chirality-selective isolation of SWCNTs. Second, we discovered that the process may be conducted in naturally occurring green solvents such as <i>p</i>-cymene, thus avoiding the typically employed hazardous organic liquid media.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"36 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photocatalytic carbon dioxide (CO2) reduction in synergism with biomass-based alcohol conversion is a sustainable strategy to maintain a carbon-neutral cycle along with the synthesis of fine chemicals. Herein, we report a heterostructure of potassium (K+) intercalated carbon nitride (K-CN) with Bi2MoO6 (BMO) forming a Z-scheme BMO/K-CN as photocatalyst. We observed that the 5BMO/K-CN heterostructure achieves the highest CO production rate (21 mmol g–1h–1) along with biomass-based para-methoxybenzyl alcohol (p-MeOBA) conversion to the corresponding aldehyde by 31% in 6 h under simulated solar light. AQY for the CO production at λ = 400 nm was estimated as 14.21%. Z-scheme formation was verified by X-ray photoelectron spectroscopy (XPS) measurements, electron paramagnetic resonance (EPR) studies, and photoluminescence (PL) experiment leading to better charge separation and migration that resulted in remarkable photocatalytic performance. Further, more insights regarding structure–activity correlation of 5BMO/K-CN were explored through EPR experiments. Thus, the current work features a sustainable approach for carbon upscaling and biomass conversion into solar fuels and fine chemicals using the intercalated carbon nitride system.
{"title":"Solar-Driven Low Carbon Fuel and Value-Added Chemicals: An Exemplification in Carbon Upscaling and Biomass Conversion via Bi2MoO6/K+ Intercalated Carbon Nitride Photocatalyst","authors":"Anjali Verma, Deepak Kumar Chauhan, Kamalakannan Kailasam","doi":"10.1021/acssuschemeng.4c04961","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04961","url":null,"abstract":"Photocatalytic carbon dioxide (CO<sub>2</sub>) reduction in synergism with biomass-based alcohol conversion is a sustainable strategy to maintain a carbon-neutral cycle along with the synthesis of fine chemicals. Herein, we report a heterostructure of potassium (K<sup>+</sup>) intercalated carbon nitride (K-CN) with Bi<sub>2</sub>MoO<sub>6</sub> (BMO) forming a Z-scheme BMO/K-CN as photocatalyst. We observed that the 5BMO/K-CN heterostructure achieves the highest CO production rate (21 mmol g<sup>–1</sup>h<sup>–1</sup>) along with biomass-based para-methoxybenzyl alcohol (<i>p-</i>MeOBA) conversion to the corresponding aldehyde by 31% in 6 h under simulated solar light. AQY for the CO production at λ = 400 nm was estimated as 14.21%. Z-scheme formation was verified by X-ray photoelectron spectroscopy (XPS) measurements, electron paramagnetic resonance (EPR) studies, and photoluminescence (PL) experiment leading to better charge separation and migration that resulted in remarkable photocatalytic performance. Further, more insights regarding structure–activity correlation of 5BMO/K-CN were explored through EPR experiments. Thus, the current work features a sustainable approach for carbon upscaling and biomass conversion into solar fuels and fine chemicals using the intercalated carbon nitride system.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-02DOI: 10.1021/acssuschemeng.4c07073
Guiying Tian, Minrui Wang, Kang Yao, Ziruo Ren, Jun Xiang, Yiming Xiao, Lei Zhang, Penggao Cheng, Jianping Zhang, Na Tang
Membrane capacitive deionization (MCDI) is a promising Li-extraction technology from salty brine to meet the growing demand for lithium sources. In this work, a Li+-selective quaternized poly(ether sulfone) coupled LiMn1.9Cr0.1O4@carbon cloth (LMC@CC/QPES) is fabricated via a rapid UV-curing method and used as the flexible Li-extraction electrode in the MCDI system. The Li-extraction results for old brine from West Taijinar confirm that the optimal capacity can reach 28.57 mg·g–1 with a retention rate of 82.36% after 200 cycles. This is ascribed to the stereoscopic carbon cloth as a current collector improving the active loading and charge transfer and the UV-curing polymer binder as a buffer layer repressing the initial manganese dissolution of spinel LiMn1.9Cr0.1O4. Importantly, the LMC@CC/QPES electrode exhibits an enhanced Li+ selectivity (Li+/Mg2+ separation coefficient > 280) through ion sieving by the spinel lattice with electrostatic repulsion by the quaternized membrane. Considering the green preparation of the Li-extraction electrode, the assembled MCDI system using QPES assisting the LMC@CC electrode can provide considerable economic benefits for lithium recovery from old brine.
{"title":"Quaternized Poly(ether sulfone) Coupled LiMn1.9Cr0.1O4@Carbon Cloth for High-Performance Membrane Capacitive Li-Extraction","authors":"Guiying Tian, Minrui Wang, Kang Yao, Ziruo Ren, Jun Xiang, Yiming Xiao, Lei Zhang, Penggao Cheng, Jianping Zhang, Na Tang","doi":"10.1021/acssuschemeng.4c07073","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07073","url":null,"abstract":"Membrane capacitive deionization (MCDI) is a promising Li-extraction technology from salty brine to meet the growing demand for lithium sources. In this work, a Li<sup>+</sup>-selective quaternized poly(ether sulfone) coupled LiMn<sub>1.9</sub>Cr<sub>0.1</sub>O<sub>4</sub>@carbon cloth (LMC@CC/QPES) is fabricated via a rapid UV-curing method and used as the flexible Li-extraction electrode in the MCDI system. The Li-extraction results for old brine from West Taijinar confirm that the optimal capacity can reach 28.57 mg·g<sup>–1</sup> with a retention rate of 82.36% after 200 cycles. This is ascribed to the stereoscopic carbon cloth as a current collector improving the active loading and charge transfer and the UV-curing polymer binder as a buffer layer repressing the initial manganese dissolution of spinel LiMn<sub>1.9</sub>Cr<sub>0.1</sub>O<sub>4</sub>. Importantly, the LMC@CC/QPES electrode exhibits an enhanced Li<sup>+</sup> selectivity (Li<sup>+</sup>/Mg<sup>2+</sup> separation coefficient > 280) through ion sieving by the spinel lattice with electrostatic repulsion by the quaternized membrane. Considering the green preparation of the Li-extraction electrode, the assembled MCDI system using QPES assisting the LMC@CC electrode can provide considerable economic benefits for lithium recovery from old brine.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142916829","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-02DOI: 10.1021/acssuschemeng.4c08608
Mei Ma, Jia-qi Bai, Huangfei Liu, Ben Liu, Zhangkai Qian, Suiqin Li, Jingshuai Chen, Mengdie Cai, Song Sun
The preparation of methyl-substituted amines by direct N-methylation of amines with CO2/H2 is an important reaction for CO2 utilization and organic synthesis. However, the design and construction of effective and stable non-noble-metal catalysts for this reaction remain challenging. Here, a cheap non-noble-Cu-based catalyst was prepared and applied in the direct N-methylation reaction of N-methylaniline with CO2 and H2. 5%Cu-ZnO(3.75%)/TiO2 showed 98.8% yield with an initial TOF of 7.7 h–1 after 24 h under 453 K, 1.5 MPa CO2, and 4.5 MPa H2, which was superior to 5%Cu/TiO2, 5%Cu/ZnO, and reported Cu-based catalysts. Furthermore, 5%Cu-ZnO(3.75%)/TiO2 can be reused at least four times and applied to the direct N-methylation of various amines with excellent selectivity. The various characterizations and experimental results showed that Cu0 was the active site, and 5%Cu-ZnO(3.75%)/TiO2 exhibited the largest surface Cu0 amount, thereby contributing to superior catalytic performance. The reaction mechanism of the direct N-methylation reaction of N-methylaniline with CO2 and H2 was proposed based on spectroscopic studies, kinetic studies, and control experiments. The reaction proceeded with the HCHO and N-methylformanilide intermediates, and the formation of HCHO from H2 and CO2 was the rate-determining step.
{"title":"Efficient Cu-ZnO/TiO2 Catalyst for Direct N-Methylation of N-Methylaniline with CO2 and H2","authors":"Mei Ma, Jia-qi Bai, Huangfei Liu, Ben Liu, Zhangkai Qian, Suiqin Li, Jingshuai Chen, Mengdie Cai, Song Sun","doi":"10.1021/acssuschemeng.4c08608","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08608","url":null,"abstract":"The preparation of methyl-substituted amines by direct <i>N</i>-methylation of amines with CO<sub>2</sub>/H<sub>2</sub> is an important reaction for CO<sub>2</sub> utilization and organic synthesis. However, the design and construction of effective and stable non-noble-metal catalysts for this reaction remain challenging. Here, a cheap non-noble-Cu-based catalyst was prepared and applied in the direct <i>N</i>-methylation reaction of <i>N</i>-methylaniline with CO<sub>2</sub> and H<sub>2</sub>. 5%Cu-ZnO(3.75%)/TiO<sub>2</sub> showed 98.8% yield with an initial TOF of 7.7 h<sup>–1</sup> after 24 h under 453 K, 1.5 MPa CO<sub>2</sub>, and 4.5 MPa H<sub>2</sub>, which was superior to 5%Cu/TiO<sub>2</sub>, 5%Cu/ZnO, and reported Cu-based catalysts. Furthermore, 5%Cu-ZnO(3.75%)/TiO<sub>2</sub> can be reused at least four times and applied to the direct <i>N</i>-methylation of various amines with excellent selectivity. The various characterizations and experimental results showed that Cu<sup>0</sup> was the active site, and 5%Cu-ZnO(3.75%)/TiO<sub>2</sub> exhibited the largest surface Cu<sup>0</sup> amount, thereby contributing to superior catalytic performance. The reaction mechanism of the direct <i>N</i>-methylation reaction of <i>N</i>-methylaniline with CO<sub>2</sub> and H<sub>2</sub> was proposed based on spectroscopic studies, kinetic studies, and control experiments. The reaction proceeded with the HCHO and <i>N</i>-methylformanilide intermediates, and the formation of HCHO from H<sub>2</sub> and CO<sub>2</sub> was the rate-determining step.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The production of urea predominantly relies on the energy-intensive Bosch–Meiser process, which operates at temperatures ranging from 150 to 200 °C and pressures of approximately 150 to 250 bar. More sustainable approaches to urea synthesis under milder conditions remain a significant challenge. Herein, we demonstrate that urea can be synthesized via a mechanochemical method using ammonia–water and CO2 under an ambient environment. Without extra catalysts, the ZrO2 texture of the jar and grinding balls has a crucial mechanocatalytic effect on direct urea synthesis. Experimental data coupled with theoretical calculation results indicate that the mechano-induced oxygen vacancies (OV) within the (101) crystal plane of ZrO2 play a pivotal role in urea formation. These vacancies notably reduce the energy barrier for the generation of *NH2 and the subsequent decomposition of NH2COOH, thereby facilitating a more energy-efficient urea synthesis process. This work presents a novel method for synthesizing urea under mild conditions, offering potential cost-effective alternatives to urea production.
{"title":"Mechanochemical Urea Synthesis Using Ammonia–Water and Carbon Dioxide Under Mild Conditions: An Experimental and Theoretical Study","authors":"Yichun Lou, Haoyu Chen, Linrui Wang, Shengpeng Chen, Yameng Song, Yifei Ding, Zixiang Hao, Chengli He, Dong Qiu, Hui Li, Junjian Wang, Duanyang Liu, Xiaoli Cui","doi":"10.1021/acssuschemeng.4c05811","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05811","url":null,"abstract":"The production of urea predominantly relies on the energy-intensive Bosch–Meiser process, which operates at temperatures ranging from 150 to 200 °C and pressures of approximately 150 to 250 bar. More sustainable approaches to urea synthesis under milder conditions remain a significant challenge. Herein, we demonstrate that urea can be synthesized via a mechanochemical method using ammonia–water and CO<sub>2</sub> under an ambient environment. Without extra catalysts, the ZrO<sub>2</sub> texture of the jar and grinding balls has a crucial mechanocatalytic effect on direct urea synthesis. Experimental data coupled with theoretical calculation results indicate that the mechano-induced oxygen vacancies (O<sub>V</sub>) within the (101) crystal plane of ZrO<sub>2</sub> play a pivotal role in urea formation. These vacancies notably reduce the energy barrier for the generation of *NH<sub>2</sub> and the subsequent decomposition of NH<sub>2</sub>COOH, thereby facilitating a more energy-efficient urea synthesis process. This work presents a novel method for synthesizing urea under mild conditions, offering potential cost-effective alternatives to urea production.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Catalytic transfer hydrogenation (CTH) strongly relies on the synergistic interaction between Lewis acid and Lewis base. Highly active, high-density, and well-dispersed Lewis acid–base pairs (LP) are crucial to achieving efficient CTH catalysis, yet forming such an ideal interface remains challenging. To address this, a novel construction strategy is presented, which leverages the regulation of the layered double hydroxide (LDH) lattice structure to establish an ideal LP interface. Supercritical isopropyl alcohol (SCIP) was employed to selectively remove hydroxyl groups and hydrogen bonds from the NiAl-LDH surface, constructing rich MCUS and Ni-OOH at the LDH interface in a simple, controllable, and environmentally friendly way. The formation process of MCUS and Ni-OOH in SCIP was analyzed using a series of dynamic characterization. Key factors restricting the formation of MCUS and Ni-OOH were identified by comparing results across different precursor preparation methods and temperatures of SCIP treatment. On this basis, the one-pot reaction system was established. Within this system, catalyst preparation and the CTH of ethyl levulinate (EL) to γ-valerolactone (GVL) co-occur. The system simplifies the CTH reaction process and exhibits ultrahigh catalytic efficiency, with a GVL formation rate of 0.780 molGVL·g–1·h–1. Compared to traditional reaction systems and catalysts, the developed one-pot reaction system and catalyst demonstrates significant advantages and exhibit excellent cyclic stability after catalyst stabilization. The combination of the LP interface and the one-pot reaction system enabled environmentally friendly, economical, and efficient biomass-based GVL synthesis.
{"title":"Lewis Acid–Base Pairs Constructed via Lattice Regulation for Ultrafast Catalytic Transfer Hydrogenation","authors":"Dongjie Zhang, Yue Zhang, Haitao Li, Yin Zhang, Peiru Zhang","doi":"10.1021/acssuschemeng.4c08109","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08109","url":null,"abstract":"Catalytic transfer hydrogenation (CTH) strongly relies on the synergistic interaction between Lewis acid and Lewis base. Highly active, high-density, and well-dispersed Lewis acid–base pairs (LP) are crucial to achieving efficient CTH catalysis, yet forming such an ideal interface remains challenging. To address this, a novel construction strategy is presented, which leverages the regulation of the layered double hydroxide (LDH) lattice structure to establish an ideal LP interface. Supercritical isopropyl alcohol (SCIP) was employed to selectively remove hydroxyl groups and hydrogen bonds from the NiAl-LDH surface, constructing rich M<sub>CUS</sub> and Ni-OOH at the LDH interface in a simple, controllable, and environmentally friendly way. The formation process of M<sub>CUS</sub> and Ni-OOH in SCIP was analyzed using a series of dynamic characterization. Key factors restricting the formation of M<sub>CUS</sub> and Ni-OOH were identified by comparing results across different precursor preparation methods and temperatures of SCIP treatment. On this basis, the one-pot reaction system was established. Within this system, catalyst preparation and the CTH of ethyl levulinate (EL) to γ-valerolactone (GVL) co-occur. The system simplifies the CTH reaction process and exhibits ultrahigh catalytic efficiency, with a GVL formation rate of 0.780 mol<sub>GVL</sub>·g<sup>–1</sup>·h<sup>–1</sup>. Compared to traditional reaction systems and catalysts, the developed one-pot reaction system and catalyst demonstrates significant advantages and exhibit excellent cyclic stability after catalyst stabilization. The combination of the LP interface and the one-pot reaction system enabled environmentally friendly, economical, and efficient biomass-based GVL synthesis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142916830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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