Article
Chemistry, Multidisciplinary
Hochul Woo, Angela M. Devlin, Adam J. Matzger
Summary: Solvent exchange within metal-organic frameworks (MOFs) is crucial for activating coordinatively unsaturated sites (CUS) and achieving optimal surface area, enabling versatile applications of MOFs. This study quantifies the exchange behavior of a copper paddlewheel-based CUS-MOF (HKUST-1) in the presence of different solvents and reveals that solvent exchange in CUS-MOFs is not diffusion-limited, but rather determined by the solvent exchange kinetics at the metal center. The insights from this study can inform best practices for solvent exchange in various copper-paddlewheel-based MOFs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Energy & Fuels
Hao Guo, Jun Cheng, Yuxiang Mao, Lei Qian, Yang Shao, Weijuan Yang
Summary: To enhance the atomic utilization of metal-organic framework in biodiesel production from high acid value microalgal lipids, a strategy using ultrafine ZIF-67 was proposed. By reducing the crystal size of ZIF-67, coordinatively unsaturated active sites, such as Co-Nx and pyridinic-N, were increased, resulting in improved Lewis acid-base properties. The optimized catalyst achieved high conversion efficiencies for free fatty acid and triglyceride in acidic lipids to bio-diesel.
Article
Energy & Fuels
Hao Guo, Jun Cheng, Yuxiang Mao, Lei Qian, Yang Shao, Weijuan Yang
Summary: In order to increase the efficiency of metal-organic frameworks for biodiesel production, ultrafine ZIF-67 was used to release metal atoms and create coordinatively unsaturated cobalt-nitrogen active sites. Reducing the crystal size of ZIF67 resulted in an increase in the unsaturated Co-N-x content, leading to enhanced Lewis acid-base properties. The optimized catalyst achieved high conversion efficiencies for free fatty acid and triglyceride in acidic lipids to biodiesel.
Article
Chemistry, Multidisciplinary
Xiaoyue Shi, Yiqi Ling, Youcong Li, Guanhua Li, Juan Li, Lingwei Wang, Fanhong Min, Rene Huebner, Shuai Yuan, Jinhua Zhan, Bin Cai
Summary: This study presents a novel approach for achieving complete glucose electrooxidation using a Cu-based metal-hydroxide-organic framework, which exhibits significantly improved electrocatalytic activity and enables the exclusive oxidation of glucose into formate and carbonate. A high-performance nonenzymatic glucose sensor was also developed. This work provides a new molecule-level strategy for designing catalytically active sites and has potential implications for the development of next-generation electrochemical devices.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
S. Rajasekaran, B. S. Reghunath, K. R. Sunaja Devi, D. Pinheiro
Summary: A bimetallic electrocatalyst MOF using Ni and Cu has been synthesized and evaluated for oxygen evolution reaction. Bimetallic MOFs show higher activity in electrocatalysis due to the abundance of active sites, local crystallinity, and lower long-range disorder. Ni-Cu MOFs exhibit a low overpotential of 340 mV at 10 mA/cm2 and a low Tafel slope of 65 mV/dec when used as oxygen evolution catalysts. The study paves the way for efficient catalyst development in water splitting applications.
MATERIALS TODAY CHEMISTRY
(2023)
Article
Chemistry, Applied
Zekun Li, Zhao Wang
Summary: Metal-organic frameworks (MOFs) are considered as promising catalyst candidates for oxygen evolution reaction (OER). This study successfully tuned the coordinatively unsaturated metal sites (CUMSs) of nickel-based MOF (Ni-BTC) using glow discharge plasma at room temperature. The electrochemical activity of Ni-BTC was correlated with the abundance of CUMSs.
Article
Multidisciplinary Sciences
Ji Wei Sun, Xuefeng Wu, Peng Fei Liu, Jiacheng Chen, Yuanwei Liu, Zhen Xin Lou, Jia Yue Zhao, Hai Yang Yuan, Aiping Chen, Xue Lu Wang, Minghui Zhu, Sheng Dai, Hua Gui Yang
Summary: The authors report a general method to synthesize coordinatively unsaturated metal-nitrogen sites doped within carbon nanotubes, which can mediate efficient CO2-to-CO formation in a membrane flow configuration, achieving high current density and CO selectivity. This fabrication method can be scaled up with negligible decay in CO2-to-CO activity.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Yangpei Li, Hao Han, Aodong Xu, Yanming Fu, Chengfeng Zhu, Lanjun Cheng, Yougui Li
Summary: Integrating inorganic oxygen evolution cocatalysts with photoanodes is a viable strategy to increase the photogenerated charge utilization. In this study, a cobalt-organic complex was constructed and applied to the photoelectrochemical water oxidation. The synthesized photoanode exhibited high photocurrent density and excellent photostability.
INORGANIC CHEMISTRY
(2023)
Article
Radiology, Nuclear Medicine & Medical Imaging
Nobuhiko Iki, Ryuta Nakane, Atsuko Masuya-Suzuki, Yoshikazu Ozawa, Takako Maruoka, Megumi Iiyama, Akira Sumiyoshi, Ichio Aoki
Summary: In this study, a manganese-based metal organic framework (MOF) with a safe paramagnetic center and high relaxivity was proposed. The MOF, modified with poly(ethylene glycol), could be stably dispersed in water and passively delivered to tumor tissues. In vivo imaging showed significant signal enhancement in T1-weighted images for tumor recognition.
MOLECULAR IMAGING AND BIOLOGY
(2023)
Article
Chemistry, Applied
Chengcheng Huang, Zipeng Zhao, Enming Ping, Lijuan Zhang, Yunshan Zhou, Libo Qin
Summary: The Ag@CPO-27-Ni composites, synthesized with silver nanoparticles loaded in CPO-27-Ni, showed enhanced adsorptive desulfurization capacity compared to CPO-27-Ni. The interaction between Ag particles and sulfur-containing compounds played a key role in promoting selective attraction and improving desulfurization performance.
MICROPOROUS AND MESOPOROUS MATERIALS
(2021)
Article
Engineering, Environmental
He Liang, Ruiping Liu, Xiaoqiang An, Chengzhi Hu, Xiwang Zhang, Huijuan Liu
Summary: Recently, a new Fenton-like catalyst, CUMSs/MIL-101(Fe, Cu), with mixed valence of Fe(II)/Fe(III) and Cu(I)/Cu(II) as coordinatively unsaturated metal sites has been successfully synthesized and demonstrated enhanced degradation performance for ciprofloxacin compared to single iron catalyst in the neutral pH range. This work provides a new strategy for designing highly efficient, stable, and eco-friendly Fenton-like catalysts for superior environmental remediation efficiency across a wide pH range.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Agricultural Engineering
Hao Guo, Jun Cheng, Yuxiang Mao, Lei Qian, Yang Shao, Xiao Yang, Weijuan Yang
Summary: In this study, an acid-base bifunctional catalyst was successfully synthesized and its catalytic performance was improved through pyrolysis process. The pyrolysis process destroyed the coordination structure of the catalyst, releasing more active sites and increasing the Lewis acid/Bronsted acid ratio and basicity. Additionally, more mesopores were generated inside the catalyst, facilitating the transportation and conversion of lipid molecules. The use of this catalyst achieved higher conversion efficiency of microalgal lipids compared to traditional catalysts.
BIORESOURCE TECHNOLOGY
(2022)
Article
Environmental Sciences
Yunyun Li, Xiang Li, Bo Wang
Summary: Researchers successfully synthesized a photo-Fenton catalyst based on MIL-53 (Fe) for the effective degradation of micropollutants in water. By introducing tunable Lewis acid active sites within the cavities of MIL53 (Fe), sixteen micropollutants were effectively removed. The study also showed that the introduction of unsaturated coordinated/lewis acid sites can greatly reduce the band gap energy and increase the charge-separation efficiency, leading to improved degradation of structurally diverse pharmaceuticals with environmentally relevant concentrations.
Article
Green & Sustainable Science & Technology
Jian Sun, Tao Xue, Liying Cui, Juan Liu
Summary: This study presents a controllable bibonding method to construct coordinatively unsaturated Zni+ (0 < i < 2) active sites by forming N(g-C3N4)-Zn-N-(imidazole) under mild experimental conditions. The catalysts with Zni+ are utilized for the photo-Fenton degradation of methylene blue (MB) without any oxidant, and the degradation efficiency is positively correlated with Zni+. Zni+ improves the Fe2+/Fe3+ conversion efficiency and H2O2 generation ability of the catalysts. The optimized catalysts with 2.27% of Zni+ exhibit photo-Fenton degradation efficiency of MB as 73.45 mg g(-1) at pH 7 and 78.54 mg g(-1) at pH 4. This strategy can be applied to construct coordinatively unsaturated metal sites for a series of narrow bandgap semiconductor materials containing nitrogen atoms.
ADVANCED SUSTAINABLE SYSTEMS
(2023)
Article
Nanoscience & Nanotechnology
Wenting Ji, Fan Yang, Jianhui Sun, Rongping Xu, Peng Li, Liqiang Jing
Summary: Sensitive and selective optoelectronic detection of NO2 at ultralow concentration (ppb-level) remains challenging. In this study, Ni metal-organic frameworks/CN nanosheet heterojunctions were fabricated by electrostatic induced assembly and post-alkali etching. The optimized heterojunction exhibited a detection limitation of 1 ppb for NO2, along with outstanding selectivity and long-term stability. The superior performance was attributed to enhanced charge transfer and separation at the heterojunction interface, as well as favorable adsorption of NO2 by unsaturated Ni(II) sites.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Engineering, Chemical
Yannick Ureel, Florence H. Vermeire, Maarten K. Sabbe, Kevin M. Van Geem
Summary: Carbenium ions play important roles as intermediates in zeolite and plasma chemistry. Thermodynamic properties of these ions need to be incorporated into kinetic models, resulting in more accurate and general models for zeolite design and plasma process development.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Ana Rubio-Gaspar, Sergio Navalon, Sergio Tatay, Francisco G. Cirujano, Carmen Fernandez-Conde, Natalia M. Padial, Carlos Marti-Gastaldo
Summary: Compared to indirectly modifying the framework, synthetic control of cluster composition allows direct access to catalytic activities without specific metal combinations. In this study, the aminolysis reaction of epoxides was tested using isostructural mesoporous frameworks with five combinations of homometallic and heterobimetallic metal-oxo trimers (Fe3, Ti3, TiFe2, TiCo2, and TiNi2). Only the TiFe2 nodes displayed activities comparable to benchmark catalysts based on grafting of strong acids, which arise from the combination of Lewis Ti4+ and Bronsted Fe3+-OH acid sites. The applicability of MUV-101(Fe) in the synthesis of beta-amino alcohols was demonstrated, including the gram-scale synthesis of propranolol, a natural beta-blocker listed as an essential medicine by the World Health Organization, with excellent yield and selectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Yanfang Ding, Huanhuan Sun, Zhihao Li, Chunmei Jia, Xiaogang Ding, Can Li, Jian-Gan Wang, Zhen Li
Summary: A simple and scalable galvanic-driven strategy was used to deposit large-area Prussian Blue (PB) films on both rigid and flexible substrates. A flexible PB/Zn battery-type electrochromic device with multiple functions was constructed, including a flexible power source and capacity depletion visualization. The device exhibited excellent properties with a large optical contrast, high coloration efficiency, rapid switching, long-operation stability, and good flexibility, making it a promising flexible power source for real-world applications.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Energy & Fuels
Liang Li, Ruben van de Vijver, Kevin M. Van Geem
Summary: The gas-phase pyrolysis kinetics of syringol, an abundant component in hardwood lignin, were studied using experimental and theoretical approaches. The experimental results revealed that 2,3-dihydroxybenzaldehyde is the most important phenolic product, along with the formation of significant pyrolytic water. The proposed decomposition pathways and the findings from the kinetic model provide new insights into the chemistry of syringyl species during pyrolysis.
Article
Engineering, Chemical
Hamed Mohamadzadeh Shirazi, Arezoo Ghanbari, Florence Vermeire, Marie-Francoise Reyniers, Kevin M. Van Geem
Summary: This study compared the coking tendencies of recently developed alloys to a conventional material at a higher temperature. The results showed that aluminum-containing alloys exhibited less coke formation and better stability against aging compared to non-aluminum-containing alloys. The protective oxide surface layer of the aluminum-containing alloys remained durable and showed no signs of carburization even at high temperatures. In contrast, the conventional alloy exhibited the highest coking rate and carburization.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Green & Sustainable Science & Technology
Waheed Zeb, Martijn Roosen, Pieter Knockaert, Sven Janssens, Daniel Withoeck, Marvin Kusenberg, Joel Hogie, Pieter Billen, Serge Tavernier, Kevin M. Van Geem, Steven De Meester
Summary: Valorisation of post-consumer plastic pyrolysis oil in steam crackers and their application as precursors to chemicals is hindered by the complexity of these oils, such as boiling range, fouling risk, and contaminations. Vacuum distillation effectively improved most properties of the distilled fractions, making it an essential downstream process step for the application of post-consumer plastic pyrolysis oils as feedstock in steam crackers and precursors to chemicals.
JOURNAL OF CLEANER PRODUCTION
(2023)
Review
Thermodynamics
Mehrdad Seifali Abbas-Abadi, Yannick Ureel, Andreas Eschenbacher, Florence H. Vermeire, Robin John Varghese, Jogchum Oenema, Georgios D. Stefanidis, Kevin M. Van Geem
Summary: Is full recyclability of polyolefins via chemical recycling a dream, or can it become a reality? The main problem in recycling plastic waste is its complexity and the need for large investments in sorting and purifying solutions. Novel chemical recycling processes can offer solutions to overcome these challenges and achieve higher value products. Thermal pyrolysis and catalytic pyrolysis have shown promise in this regard, but further research is needed to optimize the process and improve the purification and catalyst stability.
PROGRESS IN ENERGY AND COMBUSTION SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Dieter Ruijten, Thomas Narmon, Korneel Van Aelst, Hanne De Weer, Robbe van der Zweep, Tessy Hendrickx, Claude Poleunis, Lingfeng Li, Kevin M. Van Geem, Damien P. Debecker, Bert F. Sels
Summary: Functionalization of bio-based aromatics offers a renewable way of fulfilling chemical and materials needs. A Cu-catalyzed hydrogen borrowing strategy successfully functionalizes aliphatic alcohols in aromatic monomers and dimers derived from lignin. The stable lignin-derived tertiary amines display excellent antioxidant activity, highlighting the value of the hydrogen borrowing upgrading strategy.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Engineering, Chemical
Eli K. C. Moens, Yoshi W. Marien, Alessandro D. Trigilio, Kevin M. Van Geem, Paul H. M. Van Steenberge, Dagmar R. D'hooge
Summary: As interest in recycling plastics grows, it becomes increasingly important to model the thermochemical recycling of vinyl polymers. However, there are fewer studies on the convergence of simulation results in this field compared to polymerization or polymer reaction engineering. Using the coupled matrix-based Monte Carlo (CMMC) framework, it is shown that similar convergence demands can be employed, but with threshold values for average relative error predictions. The effect of initial chain length and number of defects on convergence demands is studied using theoretical feedstocks generated from CMMC polymer synthesis simulations.
Article
Engineering, Environmental
Evangelos Delikonstantis, Panagiotis Vettas, Fabio Cameli, Marco Scapinello, Anton Nikiforov, Guy B. Marin, Kevin M. Van Geem, Georgios D. Stefanidis
Summary: The conversion of CO2 in steel mill off-gases to syngas using nanosecond pulsed discharges at atmospheric pressure is an effective way to reduce the environmental impact of the steelmaking process. Experimental results show that CO2 conversion is affected by H2 excess, interelectrode distance, and specific energy input (SEI). It is recommended to use a stoichiometric H2:CO2 feed ratio for higher energy efficiency.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Thermodynamics
L. dos S. Vargette, N. D. Ristic, M. Geerts, G. J. Heynderickx, G. B. Marin, K. M. Van Geem
Summary: The use of heavier feedstocks presents challenges in the steam cracking process due to severe fouling. The Fouling Assessment SeTup (FAST) was developed to understand fouling phenomenon and its relation to feedstock composition. The experimental unit determined fouling tendency in different sections of a steam cracker and tested a mitigation concept using paraffinic fluid injection in the transfer line heat exchanger (TLE) section, which substantially reduced fouling.
HEAT AND MASS TRANSFER
(2023)
Article
Engineering, Chemical
Siyuan Chen, Paulien Malego, Kevin M. Van Geem, Yi Ouyang, Geraldine J. Heynderickx
Summary: Gas-liquid vortex units (GLVUs) have potential for solvent-based applications due to their exceptional multiphase mixing and mass transfer performance. Computational fluid dynamics (CFD) simulations are used to optimize the design of GLVU geometry and operating conditions. The optimized designs show significant improvement in gas-liquid contact time and energy consumption efficiency.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Green & Sustainable Science & Technology
Oleksii Mynko, Mike Bonheure, Ismael Amghizar, David J. Brown, Lin Chen, Guy B. Marin, Rodrigo Freitas de Alvarenga, Didem Civancik Uslu, Jo Dewulf, Kevin M. Van Geem
Summary: In the Chemical Process Industry (CPI), hydrogen production from steam methane reforming is the only process that emits more greenhouse gases than light olefins production. Various solutions have been proposed to reduce CO2 emissions from olefins production, but it is unclear which solution is the best. In this study, we conducted a life cycle assessment (LCA) to compare three highly promising solutions: a low-emission steam cracking furnace, an electrically driven RotoDynamic reactor (RDR), and a blue hydrogen-fired furnace.
JOURNAL OF CLEANER PRODUCTION
(2023)
Correction
Respiratory System
Jinhong Wu, Hao Zhang, Yongsheng Shi, Jinrong Wang, Yuling Han, Qiaoling Zhang, Ning Wang, Sha Liu, Yuehua Zhang, Huifen Zi, Fei Wang, Aihong Liu, Yuxin Song, ChunMei Jia, Yong Feng, Quanhua Liu, Liya Wan, Minghong Ji, Zhen Long, Jianfeng Huang, Li Liu, Yun Sun, Suping Tang, Xiaoyan Dong, Xiaojian Zhou, Wenhui Jiang, Li Shen, Haohua Jiang
RESPIRATORY RESEARCH
(2023)
Article
Engineering, Chemical
Michiel Van Melkebeke, Tobias De Somer, Tine Van Laere, Thien Nguyen Luu Minh, Hamed Mohamadzadeh Shirazi, Hilde Poelman, Kevin Van Geem, Steven De Meester
Summary: This study explores the potential of using adsorption in a non-aqueous environment as a novel approach for plastic waste dissolution recycling. The results suggest that activated charcoal can effectively remove dyes but has weak adsorption capacity for polystyrene. The adsorption process is predominantly driven by physical forces and is an endothermic process.
SEPARATION AND PURIFICATION TECHNOLOGY
(2024)
