Editorial Material
Chemistry, Physical
Marc Baldus, Bert M. Weckhuysen
Summary: This study demonstrates the importance of oxygenates in regulating the conversion of synthesis gas over an oxide-zeolite-based bifunctional catalyst material through advanced solid-state nuclear magnetic resonance experiments.
Article
Chemistry, Physical
Yihui Li, Ziang Zhao, Wei Lu, Miao Jiang, Cunyao Li, Min Zhao, Leifeng Gong, Shiyi Wang, Luyao Guo, Yuan Lyu, Li Yan, Hejun Zhu, Yunjie Ding
Summary: This study presents a tandem catalyst utilizing CoMn and Rh-metalated POPs for the efficient conversion of syngas into oxygenates. The catalyst shows high selectivity and yield in the production of higher oxygenates.
Article
Chemistry, Multidisciplinary
Gaofeng Chen, Yunchao Feng, Zhiwei Wang, Guihua Yan, Zhihao Si, Yong Sun, Xing Tang, Shuhua Yang, Tingzhou Lei, Xianhai Zeng, Lu Lin
Summary: The study utilized a solvent coordination-assisted impregnation strategy to synthesize CuCo@M-SiO2 catalysts, which can enhance the yield of higher alcohol synthesis. Among the selected solvent ligands, the CuCo@M-SiO2 catalyst derived from 1,2-propanediol-assisted impregnation exhibited excellent catalytic performance.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Physical
Sindhu S. Nathan, Arun S. Asundi, Adam S. Hoffman, Jiyun Hong, Chengshuang Zhou, Fernando D. Vila, Matteo Cargnello, Simon R. Bare, Stacey F. Bent
Summary: Depositing Fe2O3 modified Rh/SiO(2) catalyst by atomic layer deposition (ALD) enhances both the turnover frequency and the selectivity towards higher oxygenates, while mitigating catalyst sintering.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Tingting Qin, Tiejun Lin, Xingzhen Qi, Caiqi Wang, Liusha Li, Zhiyong Tang, Liangshu Zhong, Yuhan Sun
Summary: The synthesis of higher alcohols from syngas with high selectivity is challenging but important. This study explores a strategy to enhance the production of higher alcohols by tuning the chemical environment and utilizing synergistic relay reactions. Introducing Rh or Ru components to CoMn oxides greatly enhances CO insertion rate and catalytic activity, leading to increased selectivity for oxygenates while maintaining a high fraction of C-2+OH. Multiple studies show that the dispersed Rh delta+ or Ru delta+ species effectively tune the chemical environment and promote stable Co2C existence, catalyzing the coupling of syngas and in-situ generated olefins to produce additional oxygenates via hydroformylation route. The synergistic effect of Co-0, Co2C, and Rh delta+ (or Ru delta+) species, along with the promotional effect of olefins relay reaction, contribute to improving both higher alcohols selectivity and CO conversion.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Multidisciplinary Sciences
Ming Zhang, Rammile Ettelaie, Lianlian Dong, Xiaolong Li, Ting Li, Xiaoming Zhang, Bernard P. Binks, Hengquan Yang
Summary: A practical one-pot cascade catalysis method was developed by combining Pickering emulsions with continuous flow. The co-localization of catalytically active sub-compartments within droplets of a Pickering emulsion resulted in cell-like microreactors, which showed enhanced catalysis efficiency and controlled kinetics of cascade catalysis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Hiroyuki Mutoh, Shu Nakamura, Koichi Hagiwara, Masayuki Inoue
Summary: Limonoids 1 and 2 share a 6/6/6/5-membered ABCD ring system and a six-membered oxacycle, but differ in their C9-stereochemistries. A novel radical-based strategy was developed to construct the pentacyclic skeletons of 1 and 2, by coupling oxacycle-fused A-ring and enyne fragments to produce radical precursors 4a-4c with different C7-oxygen functionalities, which then participated in a radical cascade reaction to cyclize the C9-diastereomeric BCD rings.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Editorial Material
Chemistry, Physical
Michael Claeys
Summary: Double-shelled hollow spheres comprised of various catalytic materials enhance the efficiency of catalytic processes for the selective conversion of hydrogen and carbon monoxide to gasoline.
Article
Chemistry, Physical
Xingzhen Qi, Tiejun Lin, Kun Gong, Xinxing Wang, Dong Lv, Fei Yu, Yunlei An, Zhiyong Tang, Liangshu Zhong
Summary: This study achieved the conversion of syngas into higher oxygenates using ZnO-modified CoMn-based catalysts, and found that the addition of Zn can effectively regulate the catalytic behavior and structure evolution, leading to improved selectivity and yield of oxygenates.
APPLIED CATALYSIS A-GENERAL
(2022)
Article
Chemistry, Physical
Songyue Han, Dong Fan, Nan Chen, Wenhao Cui, Linhai He, Peng Tian, Zhongmin Liu
Summary: An efficient and stable triple-tandem catalyst system has been developed for the conversion of syngas into ethanol. The system achieved high CO conversion (52%) and high selectivity to ethanol (62%), resulting in a remarkably high ethanol space-time yield of 6.5 mmol g(-1) h(-1).
Article
Chemistry, Physical
Calton J. Kong, Emily L. Warren, Ann L. Greenaway, Rajiv Ramanujam Prabhakar, Adele C. Tamboli, Joel W. Ager
Summary: Cascade photoelectrocatalysis involves coupling different CO2 reduction catalysts to different branches to enhance the selectivity of solar-driven CO2 reduction. Design principles include tuning photocurrents and photovoltages to facilitate the target reaction.
SUSTAINABLE ENERGY & FUELS
(2021)
Article
Chemistry, Multidisciplinary
Zhuang Zeng, Zhuoshi Li, Shaoxia Guo, Jing Lv, Shouying Huang, Yue Wang, Xinbin Ma
Summary: The Au-Fe2.2C Janus catalyst, derived from monodisperse Janus Au-Fe3O4 nanoparticles with different Fe/Au ratios, shows superior performance in higher alcohol synthesis with high space time yield and excellent catalytic stability, attributed to its unique structure and synergistic effect of CO adsorption behavior.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Bo Wu, Tiejun Lin, Min Huang, Shenggang Li, Ji Li, Xing Yu, Ruoou Yang, Fanfei Sun, Zheng Jiang, Yuhan Sun, Liangshu Zhong
Summary: A bimetallic catalyst PdCu/Z-5 was developed for the selective oxidation of methane to oxygenates at low temperature, achieving high yield and selectivity through the synergistic effect of PdO nanoparticles and Cu single atoms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Bo Wu, Min Huang, Xing Yu, Jin Liu, Tiejun Lin, Liangshu Zhong
Summary: Selective oxidation of methane to oxygenates using low-cost and environment-friendly molecular oxygen (O-2) under mild reaction conditions is a promising strategy but still remains a grand challenge. In this concept, the recent progresses for selective oxidation of methane to oxygenates using O-2 based on tandem catalysis by coupling with in situ generation of hydrogen peroxide were summarized. The remaining challenges and future perspectives for selective oxidation of methane to oxygenates via tandem catalysis were also proposed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Engineering, Chemical
Devaiah Damma, Thirupathi Boningari, Panagiotis G. Smirniotis
Summary: In this study, a series of co-promoted Rh-La/M/SiO2 catalysts were investigated for the synthesis of oxygenates from syngas. It was found that the catalysts exhibited excellent selectivity towards oxygenates by suppressing hydrocarbons formation at lower reaction temperatures. Rhodium existed as Rh2O3 on the catalyst surface, which transformed into Rh+ and Rh-0 species during the reaction. Strong synergistic effects of Rh with the promoters on the catalyst surface hindered the complete reduction of Rh3+ to metallic Rh species, contributing to higher selectivity towards oxygenates.
CHEMICAL ENGINEERING SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Marcos G. Farpon, Wilson Henao, Philipp N. Plessow, Eva Andres, Raul Arenal, Carlo Marini, Giovanni Agostini, Felix Studt, Gonzalo Prieto
Summary: A frontier challenge in single-atom catalysis is the design of fully inorganic sites that can emulate the high reaction selectivity of organometallic counterparts in homogeneous catalysis. Modulating the direct coordination environment in single-atom sites through the use of the oxide support's surface chemistry is a powerful strategy that has been underexplored. In this study, isolated Rh atoms stabilized on oxygen-defective SnO2 exhibited excellent TOF and nearly full selectivity in the gas-phase hydroformylation of ethylene, surpassing the thermodynamically favored olefin hydrogenation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Alexis Bordet, Walter Leitner
Summary: The increasing importance of green hydrogen and renewable carbon resources in sustainable chemical value chains presents challenges and opportunities for catalysts to adapt to fluctuating non-fossil energy and raw material supply. This Perspective proposes an adaptive catalysis concept based on reversibility, rapidity, and robustness (R-3 rule), and describes promising design strategies and examples for chemical energy conversion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Motlokoa Khasu, Wijnand Marquart, Patricia J. Kooyman, Charalampos Drivas, Mark A. Isaacs, Alexander J. Mayer, Sandie E. Dann, Simon A. Kondrat, Michael Claeys, Nico Fischer
Summary: The Fischer-Tropsch synthesis, traditionally associated with fossil fuel consumption, has now emerged as a key technology for converting captured CO2 and sustainable hydrogen into energy-dense fuels and chemicals. Iron-based FT catalysts with alkali and transition metal promoters show improved reducibility, activity, and selectivity. The exact speciation and location of these promoters, however, remain poorly understood.
Article
Chemistry, Multidisciplinary
Yuyan Zhang, Sami El Sayed, Liqun Kang, Matthew Sanger, Thomas Wiegand, Philip G. Jessop, Serena Debeer, Alexis Bordet, Walter Leitner
Summary: Ruthenium nanoparticles immobilized on an amine-functionalized polymer-grafted silica support can selectively catalyze the hydrogenation of bicyclic heteroaromatics. The addition of CO2 to the hydrogen gas phase can effectively shut down the arene hydrogenation reaction while maintaining activity for heteroaromatic hydrogenation. This selectivity switch is achieved through the catalytic generation of ammonium formate species on the material's surface by hydrogenation of CO2. By altering the composition of the feed gas, a variety of benzofuran and quinoline derivatives can be selectively hydrogenated to fully or partially saturated products using a single catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Wijnand Marquart, Michael Claeys, Nico Fischer
Summary: The CO2-assisted oxidative dehydrogenation reaction shows potential as a sustainable alternative for the production of light olefins. This study investigates the effect of reaction temperature on the performance of silica supported molybdenum carbide nanoparticles. The results show an increase in ethylene selectivity with reaction temperature, suggesting an oxidation/re-carburization mechanism rather than prevention of oxidation.
APPLIED CATALYSIS A-GENERAL
(2023)
Article
Chemistry, Multidisciplinary
Gabriel Durin, Mi-Young Lee, Martina A. Pogany, Thomas Weyhermueller, Nicolas Kaeffer, Walter Leitner
Summary: Electrochemical catalysis of alkyne semihydrogenation can proceed via a pathway that bypasses the hydride intermediates. The mechanism involves a nickelacyclopropene resting state followed by protonation and electron transfer steps, leading to olefin release. This approach has the potential to revolutionize hydrogenation or hydroelementation reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Environmental Sciences
Chibambila Simbeye, Caitlin Courtney, Prithvi Simha, Nico Fischer, Dyllon G. Randall
Summary: Human urine contributes a significant amount of phosphorus in domestic wastewater, and decentralized sanitation systems can be used to recover this phosphorus. This study found that the type of urine and the Fe:P molar ratio affected the yield and purity of vivianite, while the iron salt used and reaction temperature did not. The pH of the urine had the most significant impact on the solubility of vivianite. Overall, this research contributes to the knowledge on phosphorus recovery from wastewater.
SCIENCE OF THE TOTAL ENVIRONMENT
(2023)
Article
Nanoscience & Nanotechnology
Alberto Rodriguez-Gomez, Samy Ould-Chikh, Wilson Henao, Giovanni Agostini, Gonzalo Prieto, Jorge Gascon
Summary: A series of Pt-Fe catalysts supported on mesoporous silica SBA-15 were prepared and studied, showing high activity and selectivity. However, detrimental structural changes occurred after reaction-regeneration cycles, which could be minimized by reactivation.
ACS APPLIED NANO MATERIALS
(2023)
Article
Multidisciplinary Sciences
M. I. Fadlalla, R. Mohamed, D. Susac, T. M. Nyathi, S. Blair, M. Claeys, E. van Steen, P. Kooyman, J. C. Q. Fletcher, N. Fischer
Summary: One of the biggest global challenges today is providing affordable, green, sustainable energy to a growing population. Scientists and engineers are working on developing innovative technologies, such as the Power-to-X (PtX) process, which uses renewable energy, water, and captured CO2 to produce green hydrogen, liquid hydrocarbon fuels, and chemicals. These alternative technologies are important solutions, especially for sectors that are difficult to decarbonize.
SCIENTIFIC AFRICAN
(2023)
Article
Chemistry, Physical
Madita Einemann, Simon Haida, Nico Fischer, Nattawut Osakoo, Jatuporn Wittayakun, Frank Roessner
Summary: The role of cobalt chloride hexahydrate as a precursor of cobalt bulk catalysts was investigated for the Fischer-Tropsch reaction. Different oxygen-containing cobalt compounds were detected through in situ DRIFTS, in situ XANES, in situ XRD, and inverse TPR techniques. The reaction network of cobalt chloride transformation was discussed, taking into account the back mixing in different geometries of measuring cells. The choice of catalyst activation procedure is important for the formation of cobalt oxide and subsequent activity in the Fischer-Tropsch reaction.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Jeroen T. Vossen, Noah Huelsken, Andreas J. Vorholt, Walter Leitner
Summary: One way to recycle homogeneous catalysts is through multiphase catalysis, which includes not only liquid-liquid systems but also solid and liquid phases. In this study, a catalyst recycling system is presented, where the entire catalyst phase crystallizes after the reaction at ambient temperature. By using the green and polar solvent ethylene carbonate, the polar Rh/sulfoXantphos catalyst is trapped in the crystallized phase and can be recycled along with the solvent. Several reactions were performed using this system, showing high efficiency and flexibility.
Article
Chemistry, Physical
Thulani M. Nyathi, Mohamed I. Fadlalla, Nico Fischer, Andrew P. E. York, Ezra J. Olivier, Emma K. Gibson, Peter P. Wells, Michael Claeys
Summary: Co3O4 nanoparticles were supported on different TiO2 polymorphs and their catalytic performance in CO-PrOx was evaluated. Supporting Co3O4 on P25 resulted in the highest CO conversion to CO2 (72.7%), while rutile and anatase showed lower conversions (60.7% and 51.5% respectively). The reduction of Co3O4 was highest on P25 and lowest on anatase, with different crystal phases of Co-0 observed. Furthermore, the presence of different TiO2 polymorphs influenced the formation of undesired CH4 over Co-0 nanoparticles.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Hanna H. Cramer, Shubhajit Das, Matthew D. Wodrich, Clemence Corminboeuf, Christophe Werle, Walter Leitner
Summary: This article explores the stepwise catalytic reduction of CO2 to formic acid, formaldehyde, and methanol using organometallic catalysts of earth-abundant first-row metals. A linear scaling relationship is developed to map the intrinsic reactivity of transition metal pincer complexes to their activity and selectivity in CO2 hydrosilylation. The hydride affinity of the catalysts is used to predict activity/selectivity trends, and cobalt complexes with bis(phosphino)triazine PNP-type pincer ligands exhibit outstanding properties in reaching the three reduction levels selectively. The results validate the potential of tandem computational-experimental approaches in catalyst design for CO2-based chemical transformations.