Anurag Ganapathi, Mohamed Shaker and Muhammad Rabnawaz
Upcycled waxes are blended with poly(ethylene-co-vinyl acetate) (EVA) to make hot-melt adhesives (HMAs). Herein, we report partially recycled HMAs that were prepared by blending EVA with upcycled waxes obtained from mix waste polyolefins. First, waste mixed polyolefins (such as high-density, low-density, and linear low-density polyethylene and polypropylene) were converted into waxes in high yields reaching up to 92%. The obtained upcycled waxes were used as an additive for HMAs along with gum rosin. The thermal properties and seal strength of the HMAs containing upcycled waxes were compared with those of commercially available HMAs. The HMA made from upcycled wax was found to be as efficient in seal strength as the commercially available HMA. This upcycling of plastic waste for use in HMAs is yet another way of promoting circularity in single-use plastics.
{"title":"Upcycled waxes from mixed polyolefins for hot-melt adhesive (HMA) applications†","authors":"Anurag Ganapathi, Mohamed Shaker and Muhammad Rabnawaz","doi":"10.1039/D4SU00135D","DOIUrl":"10.1039/D4SU00135D","url":null,"abstract":"<p >Upcycled waxes are blended with poly(ethylene-<em>co</em>-vinyl acetate) (EVA) to make hot-melt adhesives (HMAs). Herein, we report partially recycled HMAs that were prepared by blending EVA with upcycled waxes obtained from mix waste polyolefins. First, waste mixed polyolefins (such as high-density, low-density, and linear low-density polyethylene and polypropylene) were converted into waxes in high yields reaching up to 92%. The obtained upcycled waxes were used as an additive for HMAs along with gum rosin. The thermal properties and seal strength of the HMAs containing upcycled waxes were compared with those of commercially available HMAs. The HMA made from upcycled wax was found to be as efficient in seal strength as the commercially available HMA. This upcycling of plastic waste for use in HMAs is yet another way of promoting circularity in single-use plastics.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00135d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192808","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Facing the climate crisis and planetary boundaries, research institutions must address the challenge of becoming climate-neutral and using resources more sustainably. Natural science laboratories are the most resource-intensive and CO2-emitting units within these institutions. Consequently, research groups aim to understand how to lower emissions and become sustainable by participating in green lab programs for wet labs, such as My Green Lab or LEAF. Here, we compare these programs, analyse their impact on emission savings, and give insights from conducting both programs simultaneously in our biological and chemical labs. As a centrepiece, we provide a quantitative comparison of the programs based on a Germany-wide survey of participants from both programs. We showcase the significant impact of the programs on employees' motivation to work sustainably, highlight the advantages and shortcomings of the programs, and elucidate the pitfalls of greenwashing risks and the risks of leaving the most effective measures unimplemented. Finally, we provide decision-making guidance to help scientists choose the most suitable lab sustainability program based on their individual research backgrounds, needs, and personal preferences.
{"title":"Lab Sustainability Programs LEAF and My Green Lab: impact, user experience & suitability","authors":"Bianca Ricarda Schell, Nico Bruns","doi":"10.1039/d4su00387j","DOIUrl":"https://doi.org/10.1039/d4su00387j","url":null,"abstract":"Facing the climate crisis and planetary boundaries, research institutions must address the challenge of becoming climate-neutral and using resources more sustainably. Natural science laboratories are the most resource-intensive and CO2-emitting units within these institutions. Consequently, research groups aim to understand how to lower emissions and become sustainable by participating in green lab programs for wet labs, such as My Green Lab or LEAF. Here, we compare these programs, analyse their impact on emission savings, and give insights from conducting both programs simultaneously in our biological and chemical labs. As a centrepiece, we provide a quantitative comparison of the programs based on a Germany-wide survey of participants from both programs. We showcase the significant impact of the programs on employees' motivation to work sustainably, highlight the advantages and shortcomings of the programs, and elucidate the pitfalls of greenwashing risks and the risks of leaving the most effective measures unimplemented. Finally, we provide decision-making guidance to help scientists choose the most suitable lab sustainability program based on their individual research backgrounds, needs, and personal preferences.","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To combat climate change (i.e., global warming), reducing the CO2 footprint of cement-based building materials can be substantiated by incorporating cellulosic fiber in cement matrix (fiber cement). However, such materials design imposes tremendous technical challenges towards the fabrication process, interlinked to its rheo-mechanical properties. Thus, polycarboxylate-based (petrochemical-derived) rheology modifiers and silica-based (carcinogenic) additives are usually added to the fiber-cement slurry. Micro-cellulosic biomaterials are technically a viable eco-friendly alternative, capable of modifying the rheo-mechanical properties, yet to be explored for high-density (>8 wt.% fiber) fiber cement. Herein, we have employed morphologically distinctive alpha-cellulose (AC) and microcrystalline cellulose (MCC) as rheo-mechanical additives. The total content of biomaterials in the fiber cement was up to 12 wt.%, where the ratio between the micro-cellulosic additive (AC/MCC) and the cellulosic fiber varied proportionally. As a result, various composites were fabricated based on combination 1 (AC and fiber) and 2 (MCC and fiber), and their rheo-mechanical properties were characterized to understand the effect of this morphologically distinctive micro-cellulose. Firstly, the rheological analysis revealed combination 1 reducing the yield stress (improving the workability) at any content – with 4 wt.% AC content indicating a maximum reduction in yield stress of 30%. Secondly, flexural strength analysis revealed – combinations 1 and 2 improve the modulus of rupture (MOR), and combination 2 (at 6 wt.% of MCC content) resulted in a 42% increase in MOR. Finally, we presented the cost-to-performance ratio analysis (economic perspective), highlighting the positive ramifications of this sustainable rheology modifier and additives for cement-based composite – a possible avenue for low-embodied carbon building materials without compromising the strength-to-weight ratio.
{"title":"Sustainable micro-cellulosic additives for high-density fiber cement: Emphasis on rheo-mechanical properties and cost-performance analysis","authors":"Sreenath Raghunath, Mahfuzul Hoque, Behzad Zakani, Akash Madhav Gondaliya, Johan Foster","doi":"10.1039/d4su00287c","DOIUrl":"https://doi.org/10.1039/d4su00287c","url":null,"abstract":"To combat climate change (i.e., global warming), reducing the CO2 footprint of cement-based building materials can be substantiated by incorporating cellulosic fiber in cement matrix (fiber cement). However, such materials design imposes tremendous technical challenges towards the fabrication process, interlinked to its rheo-mechanical properties. Thus, polycarboxylate-based (petrochemical-derived) rheology modifiers and silica-based (carcinogenic) additives are usually added to the fiber-cement slurry. Micro-cellulosic biomaterials are technically a viable eco-friendly alternative, capable of modifying the rheo-mechanical properties, yet to be explored for high-density (>8 wt.% fiber) fiber cement. Herein, we have employed morphologically distinctive alpha-cellulose (AC) and microcrystalline cellulose (MCC) as rheo-mechanical additives. The total content of biomaterials in the fiber cement was up to 12 wt.%, where the ratio between the micro-cellulosic additive (AC/MCC) and the cellulosic fiber varied proportionally. As a result, various composites were fabricated based on combination 1 (AC and fiber) and 2 (MCC and fiber), and their rheo-mechanical properties were characterized to understand the effect of this morphologically distinctive micro-cellulose. Firstly, the rheological analysis revealed combination 1 reducing the yield stress (improving the workability) at any content – with 4 wt.% AC content indicating a maximum reduction in yield stress of 30%. Secondly, flexural strength analysis revealed – combinations 1 and 2 improve the modulus of rupture (MOR), and combination 2 (at 6 wt.% of MCC content) resulted in a 42% increase in MOR. Finally, we presented the cost-to-performance ratio analysis (economic perspective), highlighting the positive ramifications of this sustainable rheology modifier and additives for cement-based composite – a possible avenue for low-embodied carbon building materials without compromising the strength-to-weight ratio.","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Francisco G. Cirujano, Rocio Villa, Rebeca Salas, Miguel Maireles, Nuria Martín, Belén Altava, Pedro Lozano and Eduardo García Verdugo
Catalysis is a crucial tool to efficiently address the recycling and upgrading of polymeric waste within the context of a circular economy, providing affordable and selective methods for waste valorization in alignment with the principles of green chemistry. Various catalysts, including metals, metal–organic frameworks, and biocatalysts, have been explored for the degradation of chemical poly(ethylene terephthalate) (PET) and polyurethane (PU) waste through processes like hydrolysis or alcoholysis. This critical review specifically focuses on catalytic tools, examining both homogeneous systems (such as metal salts or coordination organometallic complexes) and heterogeneous systems where the catalysts are immobilized on solids, including metal oxides, layered or porous solids, or inorganic–organic coordination polymers as well as biocatalytic counterparts from 2017 to the present. We provide a comparative analysis of the chemo-catalysts researched, evaluating their performance relative to biocatalysts using a SWOT analysis of both technologies to highlight their strengths and limitations in the context of sustainable waste management practices.
{"title":"On the metal- and bio-catalyzed solvolysis of polyesters and polyurethanes wastes","authors":"Francisco G. Cirujano, Rocio Villa, Rebeca Salas, Miguel Maireles, Nuria Martín, Belén Altava, Pedro Lozano and Eduardo García Verdugo","doi":"10.1039/D4SU00233D","DOIUrl":"10.1039/D4SU00233D","url":null,"abstract":"<p >Catalysis is a crucial tool to efficiently address the recycling and upgrading of polymeric waste within the context of a circular economy, providing affordable and selective methods for waste valorization in alignment with the principles of green chemistry. Various catalysts, including metals, metal–organic frameworks, and biocatalysts, have been explored for the degradation of chemical poly(ethylene terephthalate) (PET) and polyurethane (PU) waste through processes like hydrolysis or alcoholysis. This critical review specifically focuses on catalytic tools, examining both homogeneous systems (such as metal salts or coordination organometallic complexes) and heterogeneous systems where the catalysts are immobilized on solids, including metal oxides, layered or porous solids, or inorganic–organic coordination polymers as well as biocatalytic counterparts from 2017 to the present. We provide a comparative analysis of the chemo-catalysts researched, evaluating their performance relative to biocatalysts using a SWOT analysis of both technologies to highlight their strengths and limitations in the context of sustainable waste management practices.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00233d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192807","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qaisar Maqbool, Klaus Dobrezberger, Julian Stropp, Martin Huber, Karl-Leopold Kontrus, Anna Aspalter, Julie Neuhauser, Thomas Schachinger, Stefan Löffler, Günther Rupprechter
Carbon dioxide (CO2) and carbon monoxide (CO) hydrogenation to methane (CH4) or methanol (CH3OH) is a promising pathway to reduce CO2 emissions and to migitate dependence on rapidly depleting fossil fuels. Along these lines, a series of catalysts comprising copper (Cu) or palladium (Pd) nanoparticles (NPs) supported on zinc oxide (ZnO), as well as bimetallic CuPd NPs supported on ZnO or graphene were synthesized via various methodologies. The prepared catalysts underwent comprehensive characterization via high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX) mapping, electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), hydrogen temperature-programmed reduction and desorption (H2-TPR, -TPD), and deuterium temperature-programmed desorption (D2O-TPD). In the CO2 hydrogenation process carried out at 20 bar and elevated temperatures (300 to 500°C), Cu, Pd, and CuPd NPs (<5wt.% loading) supported on ZnO or graphene predominantly yielded CH4 as primary product, with CO generated as a byproduct via the reverse water gas shift (RWGS) reaction. For CO hydrogenation between 400 and 500°C , the CO conversion was at least 40% higher than that of CO2 conversion, with CH4 and CO2 identified as main products, the latter from water gas shift. Employing 90wt.% Cu on ZnO led to an enhanced CO conversion of 14%, with the CH3OH yield reaching 10% and the CO2 yield reaching 4.3% at 230°C. Overall, the results demonstrate that lower Cu/Pd loading (<5wt.%) supported on ZnO/graphene favored CH4 production, while higher Cu content (90wt.%) promoted CH3OH production, both for CO2 and CO hydrogenation at high pressure.
将二氧化碳(CO2)和一氧化碳(CO)加氢转化为甲烷(CH4)或甲醇(CH3OH)是减少二氧化碳排放和摆脱对快速枯竭的化石燃料依赖的一条可行途径。根据这一思路,研究人员通过各种方法合成了一系列催化剂,包括以氧化锌(ZnO)为载体的铜(Cu)或钯(Pd)纳米颗粒(NPs),以及以 ZnO 或石墨烯为载体的双金属 CuPd NPs。制备的催化剂通过高分辨率透射电子显微镜(HRTEM)、能量色散 X 射线光谱(EDX)图谱、电子能量损失光谱(EELS)、X 射线衍射(XRD)、氢温度编程还原和解吸(H2-TPR,-TPD)以及氘温度编程解吸(D2O-TPD)进行了全面表征。在 20 巴和高温(300 至 500 摄氏度)条件下进行的 CO2 加氢过程中,ZnO 或石墨烯上的 Cu、Pd 和 CuPd NPs(5wt.% 负载)主要以 CH4 为主要产物,而 CO 则通过反向水气变换(RWGS)反应作为副产物生成。在 400 至 500°C 的 CO 加氢过程中,CO 的转化率比 CO2 的转化率高出至少 40%,CH4 和 CO2 被确定为主要产物,后者来自水气变换。在氧化锌上使用 90wt.% 的铜可使 CO 转化率提高 14%,在 230°C 时,CH3OH 产率达到 10%,CO2 产率达到 4.3%。总之,研究结果表明,ZnO/石墨烯上较低的铜/钯负载量(<5wt.%)有利于产生 CH4,而较高的铜含量(90wt.%)则促进了 CH3OH 的产生,无论是 CO2 还是 CO 在高压下的氢化。
{"title":"Bimetallic CuPd Nanoparticles Supported on ZnO or Graphene for CO2 and CO Conversion to Methane and Methanol","authors":"Qaisar Maqbool, Klaus Dobrezberger, Julian Stropp, Martin Huber, Karl-Leopold Kontrus, Anna Aspalter, Julie Neuhauser, Thomas Schachinger, Stefan Löffler, Günther Rupprechter","doi":"10.1039/d4su00339j","DOIUrl":"https://doi.org/10.1039/d4su00339j","url":null,"abstract":"Carbon dioxide (CO2) and carbon monoxide (CO) hydrogenation to methane (CH4) or methanol (CH3OH) is a promising pathway to reduce CO2 emissions and to migitate dependence on rapidly depleting fossil fuels. Along these lines, a series of catalysts comprising copper (Cu) or palladium (Pd) nanoparticles (NPs) supported on zinc oxide (ZnO), as well as bimetallic CuPd NPs supported on ZnO or graphene were synthesized via various methodologies. The prepared catalysts underwent comprehensive characterization via high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX) mapping, electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), hydrogen temperature-programmed reduction and desorption (H2-TPR, -TPD), and deuterium temperature-programmed desorption (D2O-TPD). In the CO2 hydrogenation process carried out at 20 bar and elevated temperatures (300 to 500°C), Cu, Pd, and CuPd NPs (<5wt.% loading) supported on ZnO or graphene predominantly yielded CH4 as primary product, with CO generated as a byproduct via the reverse water gas shift (RWGS) reaction. For CO hydrogenation between 400 and 500°C , the CO conversion was at least 40% higher than that of CO2 conversion, with CH4 and CO2 identified as main products, the latter from water gas shift. Employing 90wt.% Cu on ZnO led to an enhanced CO conversion of 14%, with the CH3OH yield reaching 10% and the CO2 yield reaching 4.3% at 230°C. Overall, the results demonstrate that lower Cu/Pd loading (<5wt.%) supported on ZnO/graphene favored CH4 production, while higher Cu content (90wt.%) promoted CH3OH production, both for CO2 and CO hydrogenation at high pressure.","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Emily C. Giles, Abbey Jarvis, Alexander T. Sargent, Paul A. Anderson, Phoebe K. Allan and Peter R. Slater
The transition to widespread adoption of electric vehicles (EVs) is leading to a steep increase in lithium ion battery production around the world. With this increase it is predicted there will not only be a large increase in end of life batteries needing to be recycled, but also a substantial amount of production scrap, particularly in the early stages of gigafactory set-up. The recycling of such battery electrode materials has a number of challenges which need to be considered, in particular the delamination from the current collector and removal of the binder, e.g. mainly polyvinylidene fluoride (PVDF) for cathode materials. Traditional pyrometallurgy or hydrometallurgy approaches require multiple separation steps to obtain pure metal salts before resynthesising the cathode active material, and so can be high cost, high CO2 and high waste processes. Production scrap in particular, however, offers the potential for lower cost and lower environmental impact direct recycling processes to be employed, which preserves the manufactured value of the electrode material. To illustrate the potential of such an approach, here we demonstrate a direct recycling approach on EV production scrap cathode materials which utilises a low temperature heat treatment to decompose the binder and allow delamination of the cathode material from the Al current collector. A further higher temperature heat treatment is then employed to ensure complete binder removal and regenerate the cathode, with the results showing that the addition of a small amount of Li is required to improve electrochemical performance (first cycle discharge capacity (2.5–4.2 V) of 129(2) mA h g−1 and 146(4) mA h g−1 with 0 wt% and 10 wt% added lithium, respectively). Electrochemical performance can be further improved by increasing the upper voltage window to 4.3 V (first cycle discharge capacity of 146(4) mA h g−1 and 164(2) mA h g−1 at 2.5–4.2 V and 2.5–4.3 V, respectively).
随着电动汽车(EV)的普及,全球锂离子电池产量急剧增加。据预测,随着产量的增加,不仅需要回收的报废电池会大量增加,而且还会产生大量的生产废料,尤其是在千兆工厂建立的早期阶段。此类电池电极材料的回收利用有许多挑战需要考虑,特别是从电流收集器分层和去除粘合剂,例如阴极材料主要是聚偏二氟乙烯(PVDF)。传统的火法冶金或湿法冶金方法需要经过多个分离步骤才能获得纯金属盐,然后才能重新合成阴极活性材料,因此是一种高成本、高二氧化碳排放量和高废料的工艺。然而,生产废料为采用成本较低、对环境影响较小的直接回收工艺提供了可能性,从而保留了电极材料的制造价值。为了说明这种方法的潜力,我们在此展示了一种直接回收电动汽车生产废料阴极材料的方法,即利用低温热处理分解粘合剂,使阴极材料与铝集流器分层。结果表明,只需添加少量的锂就能提高电化学性能(第一周期放电容量(2.5-4.2 V)分别为 129(2) mA h g-1 和 146(4) mA h g-1,锂的添加量分别为 0 wt% 和 10 wt%)。通过将上限电压窗口提高到 4.3 V,可进一步提高电化学性能(在 2.5-4.2 V 和 2.5-4.3 V 下,第一周期放电容量分别为 146(4) mA h g-1 和 164(2) mA h g-1)。
{"title":"Direct recycling of EV production scrap NMC532 cathode materials†","authors":"Emily C. Giles, Abbey Jarvis, Alexander T. Sargent, Paul A. Anderson, Phoebe K. Allan and Peter R. Slater","doi":"10.1039/D4SU00389F","DOIUrl":"10.1039/D4SU00389F","url":null,"abstract":"<p >The transition to widespread adoption of electric vehicles (EVs) is leading to a steep increase in lithium ion battery production around the world. With this increase it is predicted there will not only be a large increase in end of life batteries needing to be recycled, but also a substantial amount of production scrap, particularly in the early stages of gigafactory set-up. The recycling of such battery electrode materials has a number of challenges which need to be considered, in particular the delamination from the current collector and removal of the binder, <em>e.g.</em> mainly polyvinylidene fluoride (PVDF) for cathode materials. Traditional pyrometallurgy or hydrometallurgy approaches require multiple separation steps to obtain pure metal salts before resynthesising the cathode active material, and so can be high cost, high CO<small><sub>2</sub></small> and high waste processes. Production scrap in particular, however, offers the potential for lower cost and lower environmental impact direct recycling processes to be employed, which preserves the manufactured value of the electrode material. To illustrate the potential of such an approach, here we demonstrate a direct recycling approach on EV production scrap cathode materials which utilises a low temperature heat treatment to decompose the binder and allow delamination of the cathode material from the Al current collector. A further higher temperature heat treatment is then employed to ensure complete binder removal and regenerate the cathode, with the results showing that the addition of a small amount of Li is required to improve electrochemical performance (first cycle discharge capacity (2.5–4.2 V) of 129(2) mA h g<small><sup>−1</sup></small> and 146(4) mA h g<small><sup>−1</sup></small> with 0 wt% and 10 wt% added lithium, respectively). Electrochemical performance can be further improved by increasing the upper voltage window to 4.3 V (first cycle discharge capacity of 146(4) mA h g<small><sup>−1</sup></small> and 164(2) mA h g<small><sup>−1</sup></small> at 2.5–4.2 V and 2.5–4.3 V, respectively).</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00389f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bernard C. Ekeoma, Jason E. Bara and James D. Sheehan
Catalytic reductive processes facilitate deconstruction of lignins into value-added aromatics. This study explores the novel use of glycerol-derived ethers (GDEs), specifically 1-3-dimethoxypropan-2-ol (DMP) and 1,3-diethoxypropan-2-ol (DEP), as hydrogen transfer solvents for reductive catalytic fractionation (RCF) of softwood biomass, marking a departure from conventional use of high-pressure molecular hydrogen and short-chain alcohols. The influence of process conditions, namely, batch holding time, temperature, catalyst species and dosage, solvent-to-biomass ratio, acidic medium (by acetic acid addition), and water volumes as a co-solvent on the yield of aromatic monomers and delignification were evaluated. Under optimal conditions, GDE-mediated RCF of softwood achieved aromatic monomer yields and delignification up to 24.9 wt% and 90.7 wt%, respectively. Aromatic monomers with unsaturated and oxygenated side chains were observed including value-added species, such as vanillin, isoeugenol, coniferaldehyde, eugenol, and vanillic acid. This observation contrasts with prior RCF studies applying ex situ hydrogen which yield monomers with saturated alkyl side chains (e.g., 4-propylguaiacol, 4-ethylguaiacol). Mass-based green chemistry metrics (e.g., solvent intensity, process mass intensity) demonstrate GDEs supported material-efficient, catalytic deconstruction of softwood lignins into value-added aromatic monomers. MALDI-TOF analyses of resultant lignin oils revealed the occurrence of sidechain dehydration and decarbonylation of oligomeric species. HSQC NMR of lignin oils indicated the absence of native linkages, especially β-O-4 bonds, post RCF treatment. Furanic monomers derived from carbohydrate fractions were identified and furan yields were higher under neat solvent conditions (∼8 wt%) than in the presence of redox catalyst (∼2 wt%). This study demonstrated successful and optimized utilization of GDEs as hydrogen transfer solvents for RCF of softwood biomass, resulting in competitive yields of functionalized aromatics within the confines of green chemistry.
{"title":"Glycerol-derived ethers enable hydrogen-free reductive catalytic fractionation of softwood lignin into functionalized aromatic monomers†","authors":"Bernard C. Ekeoma, Jason E. Bara and James D. Sheehan","doi":"10.1039/D4SU00441H","DOIUrl":"10.1039/D4SU00441H","url":null,"abstract":"<p >Catalytic reductive processes facilitate deconstruction of lignins into value-added aromatics. This study explores the novel use of glycerol-derived ethers (GDEs), specifically 1-3-dimethoxypropan-2-ol (DMP) and 1,3-diethoxypropan-2-ol (DEP), as hydrogen transfer solvents for reductive catalytic fractionation (RCF) of softwood biomass, marking a departure from conventional use of high-pressure molecular hydrogen and short-chain alcohols. The influence of process conditions, namely, batch holding time, temperature, catalyst species and dosage, solvent-to-biomass ratio, acidic medium (by acetic acid addition), and water volumes as a co-solvent on the yield of aromatic monomers and delignification were evaluated. Under optimal conditions, GDE-mediated RCF of softwood achieved aromatic monomer yields and delignification up to 24.9 wt% and 90.7 wt%, respectively. Aromatic monomers with unsaturated and oxygenated side chains were observed including value-added species, such as vanillin, isoeugenol, coniferaldehyde, eugenol, and vanillic acid. This observation contrasts with prior RCF studies applying <em>ex situ</em> hydrogen which yield monomers with saturated alkyl side chains (<em>e.g.</em>, 4-propylguaiacol, 4-ethylguaiacol). Mass-based green chemistry metrics (<em>e.g.</em>, solvent intensity, process mass intensity) demonstrate GDEs supported material-efficient, catalytic deconstruction of softwood lignins into value-added aromatic monomers. MALDI-TOF analyses of resultant lignin oils revealed the occurrence of sidechain dehydration and decarbonylation of oligomeric species. HSQC NMR of lignin oils indicated the absence of native linkages, especially β-O-4 bonds, post RCF treatment. Furanic monomers derived from carbohydrate fractions were identified and furan yields were higher under neat solvent conditions (∼8 wt%) than in the presence of redox catalyst (∼2 wt%). This study demonstrated successful and optimized utilization of GDEs as hydrogen transfer solvents for RCF of softwood biomass, resulting in competitive yields of functionalized aromatics within the confines of green chemistry.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00441h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192834","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andrew Simon George, Sourava Chandra Pradhan, K. N. Narayanan Unni and Suraj Soman
We have custom-engineered dye-sensitized solar cells (DSCs) by eliminating spacers and holes, fabricating hole-free, spacer-free (HF-SF) DSCs with a 96% active area to total area ratio. These newly engineered HF-SF dye cells provide better scalability, lower cost, and improved aesthetics with enhanced device performance delivering more than 30% efficiency under indoor/ambient illumination. Two serially interconnected HF-SF DSCs fabricated using D35:XY1b co-sensitized organic dyes and [Cu(I/II)(dmp)2] electrolyte were able to autonomously power an indoor temperature and humidity monitoring unit free of batteries at realistic indoor illumination intensities below 200 lux.
{"title":"Engineered hole-free, spacer-free dye-sensitized light harvesters for indoor photovoltaic and self-powered applications†","authors":"Andrew Simon George, Sourava Chandra Pradhan, K. N. Narayanan Unni and Suraj Soman","doi":"10.1039/D4SU00434E","DOIUrl":"10.1039/D4SU00434E","url":null,"abstract":"<p >We have custom-engineered dye-sensitized solar cells (DSCs) by eliminating spacers and holes, fabricating hole-free, spacer-free (HF-SF) DSCs with a 96% active area to total area ratio. These newly engineered HF-SF dye cells provide better scalability, lower cost, and improved aesthetics with enhanced device performance delivering more than 30% efficiency under indoor/ambient illumination. Two serially interconnected HF-SF DSCs fabricated using D35:XY1b co-sensitized organic dyes and [Cu<small><sup>(I/II)</sup></small>(dmp)<small><sub>2</sub></small>] electrolyte were able to autonomously power an indoor temperature and humidity monitoring unit free of batteries at realistic indoor illumination intensities below 200 lux.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00434e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192836","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Compressed carbon dioxide energy storage (CCES) emerges as a promising alternative among various energy storage solutions due to its numerous advantages, including straightforward liquefaction, superior energy storage density, and environmental compatibility. This review delves into the recent advancements, economic viability, technological feasibilities, and operational aspects of CCES systems comprehensively. It encapsulates the evaluation methodologies, examines the intricacies of compressed carbon dioxide storage, and explores the avenues for performance optimization within CCES technology. A comparative analysis reveals that among trans-critical, supercritical, and liquid CCES systems, the supercritical variant exhibits enhanced thermodynamic properties and a more straightforward configuration, positioning it as the preferred choice for large-scale applications. Additionally, this review incorporates recent advancements in CO2-related conversion technologies, such as photocatalytic and photothermal CO2 reduction, which further enhance the potential of CCES systems. The review highlights the future direction for CCES development, emphasizing the need for optimal compression–expansion ratios, refined analytical models, and integrated multi-disciplinary approaches. This discussion aims to serve as a foundational reference for the effective design and implementation of CCES systems.
{"title":"Advancements and assessment of compressed carbon dioxide energy storage technologies: a comprehensive review","authors":"Hailing Ma, Yao Tong, Xiao Wang and Hongxu Wang","doi":"10.1039/D4SU00211C","DOIUrl":"10.1039/D4SU00211C","url":null,"abstract":"<p >Compressed carbon dioxide energy storage (CCES) emerges as a promising alternative among various energy storage solutions due to its numerous advantages, including straightforward liquefaction, superior energy storage density, and environmental compatibility. This review delves into the recent advancements, economic viability, technological feasibilities, and operational aspects of CCES systems comprehensively. It encapsulates the evaluation methodologies, examines the intricacies of compressed carbon dioxide storage, and explores the avenues for performance optimization within CCES technology. A comparative analysis reveals that among <em>trans</em>-critical, supercritical, and liquid CCES systems, the supercritical variant exhibits enhanced thermodynamic properties and a more straightforward configuration, positioning it as the preferred choice for large-scale applications. Additionally, this review incorporates recent advancements in CO<small><sub>2</sub></small>-related conversion technologies, such as photocatalytic and photothermal CO<small><sub>2</sub></small> reduction, which further enhance the potential of CCES systems. The review highlights the future direction for CCES development, emphasizing the need for optimal compression–expansion ratios, refined analytical models, and integrated multi-disciplinary approaches. This discussion aims to serve as a foundational reference for the effective design and implementation of CCES systems.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00211c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andrea Rodil, Ingemar von Ossowski, Mari Nyyssönen, Yufang Tian, Marleen Hallamaa, Jan Deska, Malin Bomberg, Silvan Scheller
Research at the frontiers of science is getting increasingly specialised. At the same time, major global challenges require the cooperation and innovation of different research fields. One solution for enhancing scientific discovery and innovation within this landscape is to form research consortia that bring together expertise from different disciplines. Such multidisciplinary efforts are also highly recognized and increasingly enforced by funding agencies. Within this landscape, we established a research consortium consisting of three partners to explore environmental acid-tolerant formate dehydrogenases as novel biocatalysts for formic acid production from CO2. Taking our ambitious project on biocatalytic CO2 valorisation as a case study, we reflect on the realities of forming a research consortium, highlighting some of the related theoretical and technical issues, as well as its intrinsic positive and valuable nourishing effect on researchers. Finally, we offer some constructive criticism and practical advice to other scientists willing to embark on complex scientific projects through collaborations.
{"title":"Realities of the consortium approach in science: sustainable enzymatic production of C1 chemicals from carbon dioxide","authors":"Andrea Rodil, Ingemar von Ossowski, Mari Nyyssönen, Yufang Tian, Marleen Hallamaa, Jan Deska, Malin Bomberg, Silvan Scheller","doi":"10.1039/d4su00274a","DOIUrl":"https://doi.org/10.1039/d4su00274a","url":null,"abstract":"Research at the frontiers of science is getting increasingly specialised. At the same time, major global challenges require the cooperation and innovation of different research fields. One solution for enhancing scientific discovery and innovation within this landscape is to form research consortia that bring together expertise from different disciplines. Such multidisciplinary efforts are also highly recognized and increasingly enforced by funding agencies. Within this landscape, we established a research consortium consisting of three partners to explore environmental acid-tolerant formate dehydrogenases as novel biocatalysts for formic acid production from CO<small><sub>2</sub></small>. Taking our ambitious project on biocatalytic CO<small><sub>2</sub></small> valorisation as a case study, we reflect on the realities of forming a research consortium, highlighting some of the related theoretical and technical issues, as well as its intrinsic positive and valuable nourishing effect on researchers. Finally, we offer some constructive criticism and practical advice to other scientists willing to embark on complex scientific projects through collaborations.","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142192835","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}