ACS Sustainable Chemistry & Engineering最新文献

{"title":"Leaching Vanadium-Rich Steel Slag Using Carbonated Water from a Domestic SodaStream","authors":"Megan Girdwood, Aston C. Pearcy, Tanzeel Arif, Karl Dahm, Aaron T. Marshall, Chris W. Bumby","doi":"10.1021/acssuschemeng.4c08294","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08294","url":null,"abstract":"Vanadium is a “critical metal” that is predominantly produced from steelmaking slags using a salt-roast leach process that emits corrosive byproduct gases and a contaminated liquid discharge. Here, we describe a clean vanadium extraction method using the environmentally benign lixiviant–carbonated water. This method was found to be highly selective for dissolution of vanadium, manganese, and calcium over iron. By simply using saturated aqueous CO₂ solutions produced in a domestic SodaStream, we have extracted vanadium from air-roasted slags with up to 50% efficiency. A modified Parr reactor was then used to achieve higher CO₂ saturation pressures, resulting in vanadium extraction efficiencies up to 77%. Vanadium-bearing solids were precipitated from the leachate solutions and further processed to produce both vanadium metal and a V–Mn alloy. Our results demonstrate that carbonated water leaching represents a promising alternative green chemistry route to vanadium extraction from steel slags.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"53 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582635","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}

{"title":"Intermetallic PdZn Supported on Porous Carbon Derived from ZIF-8 for Efficient Direct Synthesis of H2O2","authors":"Shuzhen Lyu, Li Wang, Ruichen Liu, Rongrong Zhang, Guozhu Liu","doi":"10.1021/acssuschemeng.5c00132","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00132","url":null,"abstract":"Design of highly efficient Pd-based catalysts for the direct synthesis of hydrogen peroxide (DSHP) from H₂ and O₂ still remains a challenge. Herein, Zn-doped porous carbon was synthesized via pyrolysis of ZIF-8 under a N₂ atmosphere and then applied as supports of Pd catalysts for DSHP. The results of aberration corrected HAADF-STEM, XRD, XPS, and TEM reveal that the Zn species in the porous carbon support exist mainly in highly dispersed ZnN_<i>x</i>. In the reduction process, Zn atoms are first reduced by spillover hydrogen from adjacent Pd⁰ atoms and then diffuse into Pd particles to form intermetallic PdZn. The pyrolysis temperature appears to be a crucial factor affecting the proportion of PdZn. A catalyst supported on the porous carbon obtained at a pyrolysis temperature of 850 °C has the highest proportion of PdZn (Pd/ZnC-850). The DFT simulations reveal that intermetallic PdZn shifts the <i>d</i>-band center of Pd atoms away from the Fermi level; weakens the adsorption of O₂, *OOH, and H₂O₂; and shortens the length of the O–O bonds of *OOH and H₂O₂. These are favorable for inhibiting cleavage of O–O bonds. Pd/ZnC-850 exhibits a superior H₂O₂ selectivity (89.6%), relatively high H₂ conversion, and good stability. A H₂O₂ productivity of 44,396 mol kg_Pd^–1 h^–1 is achieved.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"86 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582631","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}

{"title":"Dual Carbon Dot Ensemble: Visible-Light-Induced Photocatalysis with Reaction Monitoring and Simultaneous Byproduct Scavenging for the ipso-Hydroxylation of Aryl Boronic Acids","authors":"Subhrajeet Banerjee, Prolay Das","doi":"10.1021/acssuschemeng.4c06581","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06581","url":null,"abstract":"Selective oxidative transformations that avoid the use of peroxides, metal catalysts, harsh conditions, toxic reagents, and solvents are indeed crucial for sustainable industrial processes. Herein, we demonstrate the engineering of a carbon dot (CD<i>pc</i>) uniquely designed to fit the profile of a photocatalyst to comply with all the above sustainability factors for the conversion of arylboronic acid to phenol, chosen as a model reaction due to its mild reaction conditions, ease of oxidation, and myriads of readily available derivatives. Additionally, arylboronic acids offer advantages over conventional phenol precursors such as benzenes or aryl halides, which are potentially more toxic and less environmentally friendly, further aligning this study with green chemistry principles. Derived from <span>l</span>-arginine, ethylenediamine, and glucose through controlled hydrothermal pyrolysis, the CD<i>pc</i> photocatalyst preserves key functional groups of the substrates on their surface. The generation of reactive oxygen species (ROS) from CD<i>pc</i> upon visible white LED light (40 W) irradiation enables the <i>ipso</i>-hydroxylation of aryl boronic acids in water at room temperature under aerobic conditions with a high yield and broad substrate scope. Control reactions performed in the presence of various radical/hole scavengers established a type I ROS mechanism to be operative involving superoxide ions. Additionally, a naphthoic acid based CD<i>ms</i> was employed to monitor the reaction in real time, taking advantage of its specificity toward boric acid, the sole byproduct of the reaction. A change in emission wavelength and hence fluorescence color from green to blue upon boric acid absorption on CD<i>ms</i> embedded in agarose beads not only enables a visual cue toward the progress of the reaction but concurrently scavenges away the boric acid, making purification easy. Thus, for the first time, a dual-CD combo is presented for efficient metal and peroxide-free photocatalysis in water with the provision of simultaneous reaction monitoring and byproduct scavenging.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582636","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}

{"title":"Ambient and Selective Electrochemical Dinitrogen Fixation to NH3 Catalyzed by Microporous Organic–Inorganic Hybrid Copper Phosphonate","authors":"Smruti Vardhan Purohit, Bibek Dash, Prashanth W. Menezes, Piyali Bhanja, Bikash Kumar Jena","doi":"10.1021/acssuschemeng.4c09790","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09790","url":null,"abstract":"Despite great efforts, developing a stable and efficient electrocatalyst with prevailing activity for the electrochemical N₂ reduction reaction (NRR) to NH₃ under ambient conditions is still a burgeoning challenge. Here, we present a new microporous organic–inorganic hybrid copper phosphonate (CuPn) electrocatalyst with outstanding stability and selectivity toward NRR. The high surface area combined with microporous channels of CuPn provides excellent faradaic efficiency of 28.32% at −0.65 V vs reversible hydrogen electrode (RHE) for NRR with a high NH₃ yield rate of 73.9 μg h^–1 mg_cat^–1 at −0.7 V vs RHE. The resulting superior catalytic activity can be ascribed to the porous structure of the material and active Cu catalytic centers. The isotopic labeling experiments and consequent qualitative and quantitative ¹H NMR analyses verified that the ammonia is derived from the electrochemical NRR process. The density functional theory (DFT) study reveals that the associative alternating pathway, with the first protonation step of *N₂ to form *NNH as the potential-determining step, offers the most favorable route for electrochemical NRR over the as-prepared microporous CuPn.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582632","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}

{"title":"Gypsum as a Feedstock for Low-Cost, Decarbonized Portland Cement and Sulfuric Acid","authors":"Samuel J. Faucher, Matthew R. Shaner, Stefan T. Omelchenko, Galit Anikeeva, Ian S. McKay","doi":"10.1021/acssuschemeng.4c08838","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08838","url":null,"abstract":"Production methods for cement and sulfuric acid are likely to change in the era of decarbonization. Cement is responsible for 8% of world carbon dioxide (CO₂) emissions and urgently needs to be decarbonized, while sulfuric acid (H₂SO₄) is produced from elemental sulfur, a fossil fuel byproduct whose supply may dwindle over time. Here, we perform a technoeconomic analysis of processes to coproduce Portland cement and sulfuric acid from gypsum via fossil-free variations of the once-prevalent Müller–Kühne (MK) process. With credit for coproduced sulfuric acid, a sulfur-driven variant of the MK process could achieve cost parity with limestone-derived cement ($40/t clinker) with dramatic (95–99%) reductions in the emission intensity. While MK process variants would saturate sulfuric acid markets well before they dominate world cement demand, these processes could simultaneously support a circular sulfur economy through valorization of gypsum waste and constitute a pathway to cost-effective decarbonized cement from a limestone-free feedstock.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"19 4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575105","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}

{"title":"Keggin-Type (Mo–V–P) Heteropolyacid-Catalyzed Selective Cleavage of β-O-4 Bond in Cotton Stalk Lignin for High Bio-Oil Yield","authors":"Andong Zhang, Yukun Ma, Sihui Mao, Ruilong Zhang, Yupeng Yuan, Jiaping Wang, Yingzhong Zhu, Zhenyu Wu, Yingqiang Sun","doi":"10.1021/acssuschemeng.5c00773","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00773","url":null,"abstract":"Depolymerization of cotton stalk lignin through catalyzing cleavage of the β-<i>O</i>-4 structure is mostly utilized for bio-oil production, while the formation of benzylic carbocations (C_α+) after the cleavage of the β-<i>O</i>-4 structure generally leads to repolymerization of monomers, resulting in low depolymerization efficiency and nonselective chemical production. Keggin-type (Mo–V–P) heteropolyacids can provide both H⁺ to catalyze the depolymerization of lignin into monomers and the subsequent methoxylation of α-OH with methanol and vanadium (V) to oxidize α-OH into α-ketones, subsequently avoiding the formation of C_α+ for repolymerization of medium products. On this basis, H₅PMo₁₀V₂O₄₀ (HPMoV₂) is first used to catalyze the decomposition of cotton stalk lignin in a methanol and water mixture. Results indicate that an optimum bio-oil yield of 58.8% with an alkane content of 30.6% is finally obtained at a temperature of 140 °C, time of 4 h, and a methanol/water ratio of 9:1. HPMoV₂-catalyzed methoxylation and oxidation of α-OH in 2-phenoxy-1-phenylethanol (PP-ol) is confirmed by the formation of 1, 2-dimethoxyethylbenzene and methyl benzoate, avoiding the formation of C_α+ with the subsequent condensation of free radicals. O₂ favors the regeneration of HPMoV₂ (V) through oxidation of HPMoV₂ (III), consequently leading to higher bio-oil yield. Moreover, addition of water is beneficial to both the dissolving of lignin and the following ring-opening and decarboxylation reactions of methyl benzoate, finally leading to a high alkane production. This work illustrates that HPMoV₂ (V) is favorable to the depolymerization of lignin with high selectivity in a methanol–water mixture, providing an efficient strategy for high-quality bio-oil production through cotton stalk lignin.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575103","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}

{"title":"Artificial Intelligence (AI) for More Sustainable Chemistry and a Greener Future","authors":"Mehran Ghasemlou, Hoang Chinh Nguyen, Sachin Talekar, Frederick M. Pfeffer, Colin J. Barrow","doi":"10.1021/acssuschemeng.5c00853","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c00853","url":null,"abstract":"This article has not yet been cited by other publications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"53 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575104","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}

{"title":"Investigation of the Degradation Phenomena of a Proton Exchange Membrane Electrolyzer Stack by Successive Replacement of Aged Components in Single Cells","authors":"Benjamin Kimmel, Tobias Morawietz, Indro Biswas, Noriko Sata, Pawel Gazdzicki, Aldo Saul Gago, Kaspar Andreas Friedrich","doi":"10.1021/acssuschemeng.4c07358","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07358","url":null,"abstract":"Due to their compactness and high flexibility to operate under dynamic conditions, proton exchange membrane water electrolyzers (PEMWEs) are ideal systems for the production of green hydrogen from renewable energy sources. For the widespread implementation of PEMWEs, an understanding of their degradation mechanism is crucial. In this work, we analyze a commercial PEMWE stack via a novel approach of breaking down from the stack to the single-cell level. Therefore, the disassembled stack components are cut to fit into single cells. Then, the aged components are successively replaced with pristine or regenerated components (cleaned and polished), and electrochemical characterizations are conducted to investigate the contributions of the individual components on performance losses. In addition, several underlying degradation phenomena are identified using different physical ex-situ analysis methods. The catalyst-coated membrane (CCM) contributes the most to performance degradation because of contamination and ionomer rearrangement. Additionally, traces of calcium, likely due to insufficient water purification used during operation or for cleaning the cell components, were found. Significant oxidation was observed on the anodic components, while the electronic conductivity on the cathode side remained unchanged. The combination of electrochemical characterization with stepwise regeneration processes and physical ex-situ analysis allows to draw conclusions about the impact of different components on degradation and to analyze the underlying aging mechanisms occurring in each component.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575356","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}

{"title":"Degradation of Microplastics by Microbial in Combination with a Micromotor","authors":"Jiaoyu Ren, Yahao Meng, Zhuxin Wang, Guangyuan Xie","doi":"10.1021/acssuschemeng.4c09593","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09593","url":null,"abstract":"Microplastics, known for their high durability, are pervasive in the environment and pose potential risks to human health via the food chain. Traditional physical and chemical degradation methods often release harmful gases and cause secondary pollution. While biodegradation is a low-carbon, ecofriendly alternative, its slow degradation remains a challenge. Research demonstrates that integrating physicochemical treatments with biological methods can enhance the efficiency of microplastic degradation; yet, major improvements are still needed. Using industrial waste fly ash and g-C₃N₄ as raw materials, we successfully fabricated MnO₂/g-C₃N₄/fly ash (MCNF) micromotors with Fenton reaction and self-propulsion capabilities through calcination and multilayer self-assembly. Notably, these micromotors do not inhibit microbial growth. Pretreatment of polystyrene (PS) with MCNF micromotors achieved a biodegradation rate of 60% within 24 days, while direct addition of MCNF micromotors enabled polyethylene (PE) degradation to reach 66% within 50 days. Compared to biodegradation alone, this combined approach increased the degradation rates of PS and PE by 40 and 24%, respectively. These findings provide a foundation for effective microplastic degradation and highlight the potential of repurposing waste resources.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560876","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}

{"title":"Modulating the Pore Hydrophobicity and Electronic Structure of Cerium MOFs for Enhanced Dimethyl Carbonate Production from CO2 and Methanol without Dehydrants","authors":"Li Xia, Dingyuan Deng, Wenzhen Wang, Yongli Yan, Dengmeng Song, Huanping Chen, Xingang Jia, Li Wang, Hongwei Ding, Yuyu Guo","doi":"10.1021/acssuschemeng.4c08623","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08623","url":null,"abstract":"The one-step synthesis of dimethyl carbonate (DMC) from methanol (MeOH) and CO₂ plays an important role in carbon neutrality, but it is still far from practical application due to the undesirable use of dehydrants and the lack of rational design of efficient catalysts. Herein, the model of a CeO₂-like cerium metal–organic framework (MOF) UiO-66-Ce-NH₂ was chosen to introduce a series of hydrophobic perfluoroalkyl groups into the –NH₂ group in the channel of the MOFs by postsynthesis modification to create a hydrophobic reaction environment and remove water molecules during the reaction process, thereby avoiding the need for additional dehydrants, denoted as UiO-66-Ce-F_<i>x</i> (<i>x</i> = 3, 5, 7, 11, and 15). As a result, the catalytic performance of UiO-66-Ce-F_<i>x</i> was significantly improved. Among them, UiO-66-Ce-F₁₁ exhibited the highest DMC formation rate of 408.25 mmol g^–1 h^–1 without additional dehydrants, which was about 13 times higher than that of unmodified UiO-66-Ce-NH₂. Importantly, to the best of our knowledge, this has reached the highest level among currently reported catalysts for the one-step synthesis of DMC from MeOH and CO₂ in batch reactors. Mechanistic studies have shown that the highly efficient catalytic performance is attributed to the synergistic effect of the hydrophobicity and electron-rich capability of the fluorides in the MOF pores. On one hand, the introduction of hydrophobic fluorides creates a hydrophobic reaction site, which accelerates the transfer of water generated in real time during the reaction out of the reaction site, thereby promoting the forward reaction kinetically. On the other hand, the electron-rich fluorides optimize the electronic structure of the Ce sites, enhancing the thermodynamic adsorption and activation of the substrates CO₂ and MeOH. In the present work, a facile post-modification strategy to realize the synergistic promoting effect of thermodynamics and kinetics of one-step synthesis of DMC from CO₂ and MeOH will offer a whole new strategy to design high-efficiency catalysts for one-step synthesis of DMC.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560702","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}