RSC sustainability最新文献

{"title":"Exsolved LaNiRuO3 perovskite-based catalysts for CO2 methanation reaction†","authors":"Ayesha A. Alkhoori, Eswaravara Prasadarao Komarala, Aasif A. Dabbawala, Aseel G. S. Hussien, Dalaver H. Anjum, Samuel Mao and Kyriaki Polychronopoulou","doi":"10.1039/D4SU00410H","DOIUrl":"https://doi.org/10.1039/D4SU00410H","url":null,"abstract":"<p >Hydrogenation of CO<small><sub>2</sub></small> for methane formation is one of the thermodynamically favorable processes for reducing atmospheric CO<small><sub>2</sub></small> emissions. The present work demonstrates the synthesis and evaluation of LaNiRuO<small><sub>3</sub></small> perovskite-derived catalysts for CO<small><sub>2</sub></small> methanation in both supported and unsupported (bulk) forms. Specifically, two catalysts were prepared: (i) a Ru-substituted LaNiO<small><sub>3</sub></small> perovskite, LaNi<small><sub>0.9</sub></small>Ru<small><sub>0.1</sub></small>O<small><sub>3</sub></small>, with 10 at% Ru and (ii) a supported version (30% LaNi<small><sub>0.9</sub></small>Ru<small><sub>0.1</sub></small>O<small><sub>3</sub></small>/Al<small><sub>2</sub></small>O<small><sub>3</sub></small>). The catalysts were synthesized through controlled reduction conditions, and they were thoroughly characterized, before and after the exsolution process, using XRD, TEM, XPS, BET, H<small><sub>2</sub></small>-TPR, and H<small><sub>2</sub></small>-TPD techniques. The characterization results indicated that the exsolved LaNi<small><sub>0.9</sub></small>Ru<small><sub>0.1</sub></small>O<small><sub>3</sub></small>/Al<small><sub>2</sub></small>O<small><sub>3</sub></small> catalyst formed small Ni particles (∼6 nm), resulting in better dispersion (18%) while maintaining a high surface area (141 m<small><sup>2</sup></small> g<small><sup>−1</sup></small>) and porosity. This catalyst demonstrated a 10% higher CO<small><sub>2</sub></small> conversion (77%) at a temperature lower by 50 °C (<em>i.e.</em> 400 °C) than the exsolved bulk LaNi<small><sub>0.9</sub></small>Ru<small><sub>0.1</sub></small>O<small><sub>3</sub></small> perovskite. Both catalysts exhibited over 90% selectivity for CH<small><sub>4</sub></small> in the 250–450 °C range. The enhanced catalytic performance of the exsolved LaNi<small><sub>0.9</sub></small>Ru<small><sub>0.1</sub></small>O<small><sub>3</sub></small>/Al<small><sub>2</sub></small>O<small><sub>3</sub></small> catalyst was attributed to the small Ni particle size, better dispersion, and the alumina support's high surface area and basic properties, facilitating the adsorption and dissociation of H<small><sub>2</sub></small> and CO<small><sub>2</sub></small>. Further long-term stability tests at 400 °C and 25 000 mL g<small><sup>−1</sup></small> h<small><sup>−1</sup></small> (WHSV) over 54 h revealed that the exsolved LaNi<small><sub>0.9</sub></small>Ru<small><sub>0.1</sub></small>O<small><sub>3</sub></small>/Al<small><sub>2</sub></small>O<small><sub>3</sub></small> catalyst maintained a 70% CO<small><sub>2</sub></small> conversion, with the CH<small><sub>4</sub></small> yield and selectivity above 60% and 95%, respectively. Thus, supporting the perovskite catalyst on Al<small><sub>2</sub></small>O<small><sub>3</sub></small> demonstrated a pronounced effect on the CO<small><sub>2</sub></small> conversion rate and CH<small><sub>4</sub","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 3866-3878"},"PeriodicalIF":0.0,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00410h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736726","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}

{"title":"Correction: Hydrothermal synthesis of ZnZrOx catalysts for CO2 hydrogenation to methanol: the effect of pH on structure and activity","authors":"Issaraporn Rakngam, Gustavo A. S. Alves, Nattawut Osakoo, Jatuporn Wittayakun, Thomas Konegger and Karin Föttinger","doi":"10.1039/D4SU90059F","DOIUrl":"10.1039/D4SU90059F","url":null,"abstract":"<p >Correction for ‘Hydrothermal synthesis of ZnZrO<small>_<em>x</em></small> catalysts for CO<small>₂</small> hydrogenation to methanol: the effect of pH on structure and activity’ by Issaraporn Rakngam <em>et al.</em>, <em>RSC Sustain.</em>, 2024, https://doi.org/10.1039/d4su00522h.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 4061-4061"},"PeriodicalIF":0.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11563206/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142649935","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}

{"title":"Cu–Mg synergy enhanced synthesis of methyl formate over noble metal-free heterogeneous catalyst systems†","authors":"Jyotishman Kaishyop, Arpan Mukherjee, Abhay Giri Goswami, Tuhin Suvra Khan and Ankur Bordoloi","doi":"10.1039/D4SU00478G","DOIUrl":"https://doi.org/10.1039/D4SU00478G","url":null,"abstract":"<p >To address the challenges associated with storage and transportation of hydrogen, Liquid Organic Hydrogen Carriers (LOHCs) like methyl formate (MF) offer a promising and sustainable solution for storing hydrogen (8.4% wt) under ambient conditions. The conversion of anthropogenic CO<small>₂</small> to MF in the presence of methanol, under base-free conditions, is attracting significant research attention, as it not only helps to limit the atmospheric CO<small>₂</small> but also produces MF as an efficient LOHC. In this study, a supported Cu nanocatalyst was synthesized, demonstrating notable activity for CO<small>₂</small> hydrogenation to MF, achieving a CO<small>₂</small> conversion of 14.01%, a turnover frequency (TOF) of 186 h<small>⁻¹</small>, and selectivity greater than 99%. These results represent the highest performance reported among noble-metal-free catalyst systems. The Cu–Mg synergy enhanced catalytic activity was thoroughly investigated in the quest for improved activity. Comprehensive characterization studies were conducted to elucidate the structure–activity relationship, and the catalyst exhibited consistent performance in recycling and long-term experiments. Additionally, a plausible reaction mechanism for the catalytic process has been proposed.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 3835-3845"},"PeriodicalIF":0.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00478g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736707","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}

{"title":"Aqueous-mediated DABCO and DABCO-ionic liquid catalysed synthesis of 3-acetylcoumarins: exploration by kinetic, electrochemical and spectroscopic studies","authors":"Arpita A. Shanbhag, Lokesh A. Shastri and Samundeeswari L. Shastri","doi":"10.1039/D4SU00465E","DOIUrl":"https://doi.org/10.1039/D4SU00465E","url":null,"abstract":"<p >A more efficient, green and user-friendly approach for the synthesis of a combinatorial library of 3-acetylcoumarins from easily available ethylacetoacetate (EAA) and <em>o</em>-hydroxyaldehydes in water at room temperature was developed with excellent yields by modifying novel methods. The experimental method is facile and more economical than traditional methods, requiring no further product purification. Furthermore, the experimental conditions were optimized at the gram scale. The catalyst was reusable, resulting in excellent yields in a shorter time. Additionally, the by-product ethanol formed in the reaction was distilled out. Interestingly, the use of DABCO, DABCO-ionic liquids and DABCO salts as catalysts yielded excellent results (95–98%) in a shorter time. All products were identified by comparing their physical and spectroscopic data. The versatility of the developed green approach encouraged us to investigate the kinetics of the slowest step in the reaction and arrive at a rate law for the reaction. The kinetic and thermodynamic experimental results prompted us to undertake spectroscopic studies, including IR and <small>¹</small>H NMR, which demonstrated that the catalyst initiated the mechanism. Additionally, cyclic voltammetry (CV), a key electroanalytical tool, showed both the spontaneity of the reaction and the tautomerism of EAA.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 4008-4027"},"PeriodicalIF":0.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00465e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736737","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}

{"title":"Unraveling the mechanism of the CO2-assisted oxidative dehydrogenation of propane over VOx/CeO2: an operando spectroscopic study†","authors":"Leon Schumacher, Marius Funke and Christian Hess","doi":"10.1039/D4SU00527A","DOIUrl":"https://doi.org/10.1039/D4SU00527A","url":null,"abstract":"<p >The CO<small>₂</small>-assisted oxidative dehydrogenation (ODH) of propane is of great interest for the usage of CO<small>₂</small> in chemical industry. Vanadia-based catalysts are a promising material class, which can replace highly toxic CrO<small>_<em>x</em></small>, the current state-of-the-art catalyst. Ceria is a commonly used support material in CO<small>₂</small> activation but has not yet been used as a vanadia support for CO<small>₂</small>-assisted propane ODH. In this study, we address the interplay between vanadia and ceria as well as the nuclearity-dependent reaction behavior of VO<small>_<em>x</em></small>/CeO<small>₂</small> catalysts using XRD, multi-wavelength Raman, UV-Vis, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). While the vanadia loading increases the selectivity, the catalysts exhibit a significant amount of side reactions, including most prominently the total oxidation over bare ceria on surface oxygen sites due to their high reducibility and propane dry reforming (PDR) over catalysts with high vanadia loading. Mechanistic analysis reveals that dimers can transfer hydrogen from propane to the ceria lattice, forming Ce–H or to a monodentate carbonate, facilitating the reverse water–gas shift reaction (RWGSR), whereas a transfer to bridged Ce–OH surface species leads to total oxidation due to the high reactivity of the formed surface species. Oligomers facilitate PDR due to their high reducibility and the active oxygen site shifts from ceria to vanadia. The catalyst can be regenerated <em>via</em> carbonates, which are highly stable and can subsequently deactivate the catalyst surface. Our results highlight the benefit of applying multiple <em>operando</em> spectroscopies to enhance the mechanistic understanding of materials relevant for CO<small>₂</small> activation and further the knowledge-based optimization of catalytic performance.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 3846-3865"},"PeriodicalIF":0.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00527a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736708","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}

{"title":"The engineering of CO2 hydrogenation catalysts for higher alcohol synthesis","authors":"Angie F. J. Tan, Muhammad Dody Isnaini, Muenduen Phisalaphong and Alex C. K. Yip","doi":"10.1039/D4SU00497C","DOIUrl":"https://doi.org/10.1039/D4SU00497C","url":null,"abstract":"<p >Anthropogenic CO<small>₂</small> emissions have drawn significant attention in recent years. Using CO<small>₂</small> as feedstock for chemical processes has become a key solution in overall closed carbon cycles for a vision of a circular carbon economy. CO<small>₂</small> hydrogenation to higher alcohols has emerged as one of the most promising CO<small>₂</small> conversion pathways for mitigating CO<small>₂</small> emissions and producing value-added chemicals. The present review critically discusses the most recent cutting-edge catalyst development in higher alcohol synthesis (HAS), focusing on the influence of different metals, promoters, and supports according to the contributions of different active species in modern catalyst configurations. Particularly, the critical roles of oxygen vacancies and the reaction mechanisms shed light on the rational design of the next-generation CO<small>₂</small> hydrogenation catalysts.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 3638-3654"},"PeriodicalIF":0.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00497c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736767","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}

{"title":"Beyond waste: cellulose-based biodegradable films from bio waste through a cradle-to-cradle approach","authors":"Mai N. Nguyen, Minh T. L. Nguyen, Marcus Frank and Dirk Hollmann","doi":"10.1039/D4SU00613E","DOIUrl":"https://doi.org/10.1039/D4SU00613E","url":null,"abstract":"<p >The basis of circular economy is the use and valorization of renewable raw materials. Especially in developing countries, crop waste such as straw and rice straw have high potential for further utilization. Within this report, we present a holistic strategy including the selective isolation of cellulose <em>via</em> simple, environmental benign two-step process. Rice straw was easily dissolved in a non-derivatizing electrolyte solvent such as aqueous solution of tetrabutylphosphonium hydroxide (TBPH) (50 wt%) at room temperature followed by precipitation in water. Quantitative amount of raw cellulose was recovered within a short period of time without heating or cooling enabling a further application of biomass material. The structure and characterization of the raw cellulose were investigated by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and by scanning (SEM) and transmission electron microscopy (TEM). This method could be an excellent alternative to the current extraction methods such as the KRAFT process. Indeed, the same chemicals as for the isolation can be used to prepare regenerated cellulose film of high purity with the raw cellulose. Due to its sustainability and exceptional biodegradability, these films have a great potential for applications in environment, textile, and separation industry. No modification of the cellulose during the extraction and preparation process occurs thus, these films are no plastics and thus can be used without regulations. In general, a full “circular economy” process is provided: valuable raw materials (cellulose) are recovered selectively from natural resources such as rice straw and further to enable products with high applicability in life (cellulose packaging film). The cradle-to-cradle process is closed by fast biodegradation of the used products.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 4028-4035"},"PeriodicalIF":0.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00613e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736720","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}

{"title":"CO2 assisted geo-polymerization: a win-win pragmatic approach for the synthesis of soda ash leading to reversal of the climate clock†","authors":"Sandeep Gupta","doi":"10.1039/D4SU00541D","DOIUrl":"https://doi.org/10.1039/D4SU00541D","url":null,"abstract":"<p >It is surprising to note that there are very few literature reports available that envisage CO<small>₂</small> utilization with sodium silicates. Our research extends this concept by integrating CO<small>₂</small> assisted utilization of fly ash with sodium silicate. The alumino-silicate polymeric material was characterized using FT-IR and NMR techniques confirming the presence of Si–O–Al and Si–O–Si linkages, which are the foundations of the hardened structure, contributing to the strength in the block. Chemical tests and spectroscopic measurements further confirmed the phase and crystallinity of the synthesized soda ash. A feasible reaction mechanism has also been proposed for the alumino-silicate polymerization, which not only leads to the formation of industrially important chemicals like Na<small>₂</small>CO<small>₃</small> (soda ash) but also results in the making of construction blocks with strengths of 11–14 MPa and water absorption of 11–15%. The presented chemical scheme utilizes a voluminous amount of CO<small>₂</small>, thereby this approach may conserve the global carbon budget, and hence it may play an important role in reversing the climate clock.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 3782-3787"},"PeriodicalIF":0.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00541d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736703","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}

{"title":"Elucidating the role of the nanostructure in protein aerogels for removal of organic water pollutants†","authors":"Rodrigo Sanches Pires, Antonio J. Capezza, David Jonsson, Jessica Lyrner Morén, Mikael S. Hedenqvist and Christofer Lendel","doi":"10.1039/D4SU00352G","DOIUrl":"https://doi.org/10.1039/D4SU00352G","url":null,"abstract":"<p >Access to efficient and affordable materials for water purification is of fundamental importance for the sustainable development of our society. Materials based on protein nanofibrils (PNFs) from agricultural waste- or side streams have recently been shown to have excellent adsorption properties for organic as well as inorganic pollutants. We here investigate the role of the nanostructure in aerogels made from whey protein isolate for the removal of a model pollutant (ibuprofen) from water. Water stable aerogels were produced using a recently developed approach for intrinsic crosslinking of protein materials without requiring additives. By comparing materials made from PNFs and from non-fibrillar whey protein we find that the fibrils have dual roles in enhancing the ibuprofen binding capacity. The PNFs do have a higher direct binding affinity but they also remodel the cell wall structures of the aerogels, resulting in a mesoporous network with enhanced ability of pollutant adsorption.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 4036-4045"},"PeriodicalIF":0.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00352g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736721","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}

{"title":"CO2 hydrogenation on ruthenium: comparative study of catalyst supports†","authors":"Göran Baade, Jens Friedland, Koustuv Ray and Robert Güttel","doi":"10.1039/D4SU00469H","DOIUrl":"https://doi.org/10.1039/D4SU00469H","url":null,"abstract":"<p >To achieve a significant reduction in anthropogenic CO<small>₂</small> in the near future, captured carbon has to be valorized. To this end, CO<small>₂</small> may be activated using H<small>₂</small> to form sustainable fuels (synthetic natural gas), platform chemicals (methanol) and higher hydrocarbons (modified Fischer–Tropsch process). In this work we synthesize Ru based catalysts from various commercially available support materials and test them under lower temperatures than usually employed at various partial pressures of CO<small>₂</small> and H<small>₂</small> using methanation as a model reaction. The results show Ru/TiO<small>₂</small>, Ru/ZrO<small>₂</small> and Ru/Al<small>₂</small>O<small>₃</small> as the most active catalysts with high activity, selectivity towards methane (&gt;95%), and stability with little to no deactivation over 80 h. These most promising catalysts are further tested and kinetic parameters determined, which find reaction orders and activation energies in agreement with literature, but differing from catalyst to catalyst, hinting at complex reaction mechanisms including the support as well as the Ru. The TOF calculated for Ru/TiO<small>₂</small> at 190 °C is 5.7 s<small>⁻¹</small> and highlights it as the most active catalyst in this work. The study opens new and promising avenues for the valorization of CO<small>₂</small>, as well as a basis to compare future optimizations and advances in the field of Ru-based CO<small>₂</small> conversion.</p>","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":" 12","pages":" 3826-3834"},"PeriodicalIF":0.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/su/d4su00469h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142736706","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}