{"title":"Chemical space-property predictor model of perovskite materials by high-throughput synthesis and artificial neural networks","authors":"Md. Ataur Rahman, Md. Shahjahan, Yaqing Zhang, Rihan Wu, Elad Harel","doi":"10.1016/j.chempr.2024.10.027","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.027","url":null,"abstract":"Lead-halide perovskites exhibit highly tunable optical properties, making them suitable for applications in photovoltaics and optoelectronics. Although considerable effort has gone into the development of methods that accurately predict the optical properties of perovskite materials based on structure, the reverse—predicting composition from optical data—is far less explored. In this study, high-throughput approaches were employed to synthesize and spectroscopically analyze a wide array of perovskites composed of mono-halide, di-halide, and tri-halides with a general formula, MA<sub>x</sub>Cs<sub>1−x</sub>Pb(Cl<sub>x</sub>Br<sub>y</sub>I<sub>1−x−y</sub>)<sub>3</sub>. The spectroscopic data were used to train an artificial neural network (ANN)-based chemical space-property predictor model designed to work with multiple responses and multiple predictors. The model predicted the chemical composition of perovskites from terahertz (THz) Raman spectroscopic data with approximately 85% accuracy. When the dataset also incorporated UV-visible spectroscopic data, the accuracy increased to nearly 92%. This study opens the possibility of real-time monitoring and defect detection, degradation analysis, and streamlined material selection and optimization of perovskite materials in industrial production.","PeriodicalId":268,"journal":{"name":"Chem","volume":"38 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142783066","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}
ChemPub Date : 2024-12-03DOI: 10.1016/j.chempr.2024.10.028
Boyang Zhang, Alexander B. Weberg, Andrew J. Ahn, Marta Guron, Leighton O. Jones, Michael R. Gau, George C. Schatz, Eric J. Schelter
{"title":"A sustainable cobalt separation with validation by techno-economic analysis and life-cycle assessment","authors":"Boyang Zhang, Alexander B. Weberg, Andrew J. Ahn, Marta Guron, Leighton O. Jones, Michael R. Gau, George C. Schatz, Eric J. Schelter","doi":"10.1016/j.chempr.2024.10.028","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.028","url":null,"abstract":"Sustainable, cost-effective cobalt/nickel separations chemistry contributes to the realization of economically competitive lithium-ion battery recycling, as well as primary mining of cobalt and nickel. Such improvements can address supply chain challenges for cobalt, a critical element. Herein, we disclose a simple method for separating Co/Ni by second coordination-sphere molecular recognition. Selective cobalt precipitation is achieved using carbonate ions in an ammonia solution due to the outer-sphere, hydrogen bonding interactions between [Co(NH<sub>3</sub>)<sub>6</sub>]<sup>3+</sup> and CO<sub>3</sub><sup>2−</sup>, evaluated with density functional theory calculations. We demonstrate this method on mixtures of Co/Ni chlorides comprising a 10-fold excess of Ni and provide comparisons with ore-processing systems. High purities (99.4(3)% Co; 98.2(4)% Ni) and recoveries (77(8)% Co; ∼100% Ni) were observed for both Co- and Ni-enriched products using optimized conditions. This method is potentially economically competitive based on initial techno-economic analysis (TEA) and life-cycle assessment (LCA) that also illustrate advantages in terms of sustainability.","PeriodicalId":268,"journal":{"name":"Chem","volume":"9 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760253","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}
ChemPub Date : 2024-12-03DOI: 10.1016/j.chempr.2024.10.024
Ruozhou Huang, Yuping Wang
{"title":"Ordered [2]catenanes in covalent organic frameworks: From molecules to materials","authors":"Ruozhou Huang, Yuping Wang","doi":"10.1016/j.chempr.2024.10.024","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.024","url":null,"abstract":"In a recent issue of <em>Chem</em>, an innovative approach for the synthesis of crystalline [2]catenane-containing covalent organic frameworks was developed. This breakthrough elucidates how the dynamics of microscopic, interlocked components influence material properties, thereby advancing the design of two-dimensional materials with sophisticated topological features.","PeriodicalId":268,"journal":{"name":"Chem","volume":"116 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760252","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}
ChemPub Date : 2024-12-02DOI: 10.1016/j.chempr.2024.10.029
Huai Qin Fu, Tingting Yu, Jessica White, Ji Wei Sun, Yuming Wu, Wen Jing Li, Nicholas M. Bedford, Yun Wang, Thomas E. Rufford, Cheng Lian, Porun Liu, Hua Gui Yang, Huijun Zhao
{"title":"Amorphous CuSbOx composite-catalyzed electrocatalytic reduction of CO2 to CO: CO2 demand-supply-regulated performance","authors":"Huai Qin Fu, Tingting Yu, Jessica White, Ji Wei Sun, Yuming Wu, Wen Jing Li, Nicholas M. Bedford, Yun Wang, Thomas E. Rufford, Cheng Lian, Porun Liu, Hua Gui Yang, Huijun Zhao","doi":"10.1016/j.chempr.2024.10.029","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.029","url":null,"abstract":"The path to practical production of targeted chemicals and fuels application via carbon dioxide reduction reactions (CO<sub>2</sub>RRs) remains a significant challenge mainly due to low CO<sub>2</sub> solubility. Aiming to tackle this key issue, herein, we used the CuSbO<sub>x</sub> cathode-catalyzed reduction of CO<sub>2</sub> to CO as a model system to quantitatively depict CO<sub>2</sub> demand-supply and performance relationships. We propose a cathode/electrolyte interface model consisting of a porous catalyst layer, and we combined the experimental and computational COMSOL Multiphysics finite-element studies to quantitatively unveil CO<sub>2</sub> demand-supply relationships and determine the maximum CO<sub>2</sub> supply capacity in both stationary H cell and gas diffusion electrode (GDE) flow cell. This work exemplifies that experimentally measured catalytic performance may not accurately reflect the maximum capacity/intrinsic electrocatalytic activity of electrocatalysts and reveals that CO<sub>2</sub> supply capacity in the GDE flow cell can be dramatically affected by the thickness of the liquid layer between the hydrophobic gas diffusion layer and the catalyst layer.","PeriodicalId":268,"journal":{"name":"Chem","volume":"3 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142758663","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}
ChemPub Date : 2024-11-29DOI: 10.1016/j.chempr.2024.10.025
Amol Uttam Pawar, Ramesh Poonchi Sivasankaran, Long Yang, Don Keun Lee, Young Soo Kang
{"title":"A methodical strategy for achieving efficient electro-solar reduction, incorporating appropriate in situ techniques","authors":"Amol Uttam Pawar, Ramesh Poonchi Sivasankaran, Long Yang, Don Keun Lee, Young Soo Kang","doi":"10.1016/j.chempr.2024.10.025","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.025","url":null,"abstract":"Solar-to-fuel production via the carbon dioxide (CO<sub>2</sub>) reduction reaction (CO2RR) is a crucial and widely discussed topic, particularly in the context of climate change. Electro-solar approaches, such as electrochemical (EC), photochemical (PC), and photoelectrochemical (PEC) methods, are promising for CO2RR due to their efficiency and mild operating conditions. The process of converting CO<sub>2</sub> into valuable products involves multiple steps and requires a deep understanding of reaction mechanisms and product selectivity. <em>In situ</em> and <em>operando</em> spectroscopic techniques are essential for elucidating these mechanisms. This review focuses on advanced <em>in situ</em> spectroscopic methods, such as X-ray absorption spectroscopy (XAS), infrared (IR) spectroscopy, Raman spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy, which provide insights into CO<sub>2</sub> adsorption, activation, and electron-proton transfer, leading to intermediate radical formation. Additionally, advanced X-ray techniques are briefly discussed, offering refined approaches to studying CO2RR dynamics. These integrated techniques are crucial for designing and optimizing catalysts for efficient CO<sub>2</sub> reduction and conversion.","PeriodicalId":268,"journal":{"name":"Chem","volume":"259 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142742537","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}
ChemPub Date : 2024-11-26DOI: 10.1016/j.chempr.2024.09.032
James M. Gallagher, Joaquin Baixeras Buye, David A. Leigh
{"title":"Out-of-equilibrium compartments: Thinking inside the box","authors":"James M. Gallagher, Joaquin Baixeras Buye, David A. Leigh","doi":"10.1016/j.chempr.2024.09.032","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.032","url":null,"abstract":"Biological cells sustain an out-of-equilibrium state by harnessing energy flows across compartment boundaries. In this issue of <em>Chem</em>, Penocchio et al. quantify how out-of-equilibrium chemical reaction networks respond to compartmentalization—providing a framework on which to build and understand aspects of nonequilibrium self-assembly, molecular machinery, and other endergonic processes.","PeriodicalId":268,"journal":{"name":"Chem","volume":"4 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719061","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}
ChemPub Date : 2024-11-22DOI: 10.1016/j.chempr.2024.11.001
Jessica Liane Hübner, Gina Ruland, Florian Pietschmann, Zita Brejwo, Benjamin Paul, Peter Strasser
{"title":"Electrolyte design for high hydrogen peroxide production rates utilizing commercial carbon gas diffusion electrodes","authors":"Jessica Liane Hübner, Gina Ruland, Florian Pietschmann, Zita Brejwo, Benjamin Paul, Peter Strasser","doi":"10.1016/j.chempr.2024.11.001","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.001","url":null,"abstract":"The electrolyte design plays a key, yet underexplored, role in the two-electron oxygen reduction reaction (2e<sup>−</sup> ORR) to hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). Here, we investigate the dramatic beneficial impact of alkali metal cations (AMCs) on the H<sub>2</sub>O<sub>2</sub> production in commercial carbon gas diffusion electrode-based flow electrolyzers in single-pass and closed-loop modes using online analytics. We demonstrate previously unavailable single-pass H<sub>2</sub>O<sub>2</sub> production rates of up to 123 mg cm<sup>−2</sup> h<sup>−1</sup> with a Faraday efficiency (FE) of 96.9% at −200 mA cm<sup>−2</sup> in the presence of potassium cations, exceeding the corresponding production rate and FE in 0.1 M H<sub>2</sub>SO<sub>4</sub> by a factor of 34. Additionally, to the increased selectivity, the onset potential of the 2e<sup>−</sup> ORR shifted by 0.42 V toward a less negative potential. Furthermore, we explore and quantify the influence of multivalent metal cations (Ca<sup>2+</sup>, Mg<sup>2+</sup>, and Al<sup>3+</sup>) on the 2e<sup>−</sup> ORR.","PeriodicalId":268,"journal":{"name":"Chem","volume":"4 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684995","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}
ChemPub Date : 2024-11-22DOI: 10.1016/j.chempr.2024.10.009
Javier Corpas, Eva Rivera-Chao, Enrique M. Arpa, Miguel Gomez-Mendoza, Yuri Katayama, Victor A. de la Peña O’Shea, Céline Bouchel, Clément Jacob, Pierre-Georges Echeverria, Alessandro Ruffoni, Daniele Leonori
{"title":"Excited-state protonation and reduction enables the umpolung Birch reduction of naphthalenes","authors":"Javier Corpas, Eva Rivera-Chao, Enrique M. Arpa, Miguel Gomez-Mendoza, Yuri Katayama, Victor A. de la Peña O’Shea, Céline Bouchel, Clément Jacob, Pierre-Georges Echeverria, Alessandro Ruffoni, Daniele Leonori","doi":"10.1016/j.chempr.2024.10.009","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.009","url":null,"abstract":"The Birch reaction is a classical process used for the partial reduction of aromatics into non-conjugated cyclohexadienes that can be further functionalized. This strategy and its more modern variants are all based on an initial single-electron transfer event converting the arene into the corresponding radical anion for either protonation or hydrogen-atom transfer. Herein, we demonstrate an umpolung approach where the aromatic is first protonated to its corresponding carbocation and then reduced using the Lewis acid-base complex Et<sub>3</sub>N−BH<sub>3</sub>. This strategy requires aromatic photoexcitation so that protonation is favored by charge-transfer and driven by excited-state antiaromaticity relief. This means that aromatic excited-state basicity rather than ground-state redox potential needs to be considered when approaching reaction development. The mild conditions and the avoidance of strong reductants have enabled tolerance of functionalities generally not compatible under standard Birch conditions.","PeriodicalId":268,"journal":{"name":"Chem","volume":"37 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684996","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":"Antigen spatial-matching polyaptamer nanostructure to block coronavirus infection and alleviate inflammation","authors":"Jingqi Chen, Yuqing Li, Xueliang Liu, Hongyi Li, Jiawei Zhu, Rui Ma, Linxin Tian, Lu Yu, Jiabei Li, Zhuang Liu, Weihong Tan, Yu Yang","doi":"10.1016/j.chempr.2024.10.021","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.021","url":null,"abstract":"Preparation for the potential emergence of future human coronaviruses (HCoVs) calls for the development of versatile and effective treatment strategies. The signs and symptoms of HCoVs include an immune inflammatory response. Therefore, our study focuses on the simultaneous inhibition of HCoV infection and the alleviation of lung inflammation. Inspired by conformational epitope matching, we engineered a <em>de novo</em> antigen spatial-matching polyaptamer (ASM-pApt) nanostructure designed to align perfectly with multiple spike (S) proteins on severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pseudovirus (PsV). Compared with monovalent aptamer, the dissociation constant (K<sub>D</sub>) of the ASM-pApt nanostructure decreased by over 1,000-fold, and its viral semi-inhibitory concentration (IC<sub>50</sub>) improved by over 100,000-fold to 89.7 fM (fmol/L), indicating the effectiveness of antigen spatial matching. By loading polyphenol as anti-inflammatory drug and chitosan (CS) as an excipient, the ASM-pApt nanostructure showed anti-inflammatory and long drug retention properties. Our design shows the promise of polyaptamer as an antiviral/anti-inflammatory candidate against emerging HCoVs in the future.","PeriodicalId":268,"journal":{"name":"Chem","volume":"2 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678776","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}
ChemPub Date : 2024-11-21DOI: 10.1016/j.chempr.2024.10.023
Gabriel Sanchez-Cano, Pablo Cristobal-Cueto, Lydia Saez, Antonio Lastra, Ana Marti-Calvo, Juan José Gutiérrez-Sevillano, Sofía Calero, Sara Rojas, Patricia Horcajada
{"title":"Drinking water purification using metal-organic frameworks: Removal of disinfection by-products","authors":"Gabriel Sanchez-Cano, Pablo Cristobal-Cueto, Lydia Saez, Antonio Lastra, Ana Marti-Calvo, Juan José Gutiérrez-Sevillano, Sofía Calero, Sara Rojas, Patricia Horcajada","doi":"10.1016/j.chempr.2024.10.023","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.023","url":null,"abstract":"Water disinfection is one of the most challenging processes for public health. Nevertheless, this process can generate inorganic by-products (chlorite [ClO<sub>2</sub><sup>−</sup>] and chlorate [ClO<sub>3</sub><sup>−</sup>]) associated with human diseases. Recently, the European Union established a permissible maximum concentration of 0.25 mg⋅L<sup>−1</sup> for both oxyanions in drinking water; thus, the existing technologies have to be adapted. Here, the earliest use of metal-organic frameworks (MOFs) in the elimination of the disinfection by-products ClO<sub>2</sub><sup>−</sup> and ClO<sub>3</sub><sup>−</sup> from fresh water is presented. Among the Fe-MOFs proposed, the robust MIL-88B-NH<sub>2</sub> demonstrated exceptional oxyanions elimination capacities (100% and 30% of ClO<sub>2</sub><sup>−</sup> and ClO<sub>3</sub><sup>−</sup> in 1 and 5 min, respectively). Based on these results, a continuous-flow device based on MIL-88B-NH<sub>2</sub> was tested under simulated realistic conditions, achieving high oxyanions elimination capacities, and the reusability of the system was demonstrated. This pioneering work opens new perspectives in the implementation of MOFs in real drinking water treatment plants (DWTPs).","PeriodicalId":268,"journal":{"name":"Chem","volume":"14 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678749","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}