Review
Chemistry, Inorganic & Nuclear
Abolfazl Ghaderian, Samrana Kazim, Mohammad Khaja Nazeeruddin, Shahzada Ahmad
Summary: Energy conversion through sustainable means is crucial to combat global warming, with molecular ruthenium complexes being key in producing H-2 gas. Different categories of RWOCs have been proposed for improvements, leading to a new family of RWOCs.
COORDINATION CHEMISTRY REVIEWS
(2022)
Review
Chemistry, Multidisciplinary
P. M. Stanley, J. Haimerl, N. B. Shustova, R. A. Fischer, J. Warnan
Summary: Solar fuel production through artificial molecular photosystems is attractive due to its potential to generate sustainable clean energy. The interface between molecular constituents and metal-organic frameworks (MOFs) allows for recyclability, controlled site positioning, and insights into catalytic mechanisms.
Article
Chemistry, Multidisciplinary
Tiezheng Pan, Basudev Maity, Satoshi Abe, Taiki Morita, Takafumi Ueno
Summary: The emergence of protein-based crystalline materials provides promising opportunities for enzyme immobilization. This study demonstrates the use of polyhedra crystals to simultaneously encapsulate the foreign enzymes FDH and the organic photocatalyst eosin Y. These hybrid protein crystals, prepared easily by cocrystallization within a cell, form solid particles at a scale of 1 μm without the need for complex purification processes. The immobilized FDH within protein crystals exhibits recyclability, thermal stability, and maintains 94.4% activity compared to the free enzyme. Additionally, the incorporation of eosin Y enables CO(2)-formate conversion activity in the solid catalyst through a cascade reaction. This work highlights the potential of engineering protein crystals for the development of robust and environmentally friendly solid catalysts for artificial photosynthesis.
Article
Chemistry, Physical
Souvik Roy, Melanie Miller, Julien Warnan, Jane J. Leung, Constantin D. Sahm, Erwin Reisner
Summary: The study introduces a hybrid molecular catalyst that efficiently converts CO2 to CO with high selectivity and turnover number. In situ UV-visible spectroelectrochemical investigations reveal the catalytic mechanism. Lastly, the integration of the catalyst with a photoelectrode achieves benchmark photoelectrochemical CO reduction performance.
Review
Energy & Fuels
Matthew Sheridan, Benjamin D. Sherman, Yi Xie, Ying Wang
Summary: Research on ruthenium-based molecular complexes as catalysts for light-driven water splitting shows promising results, with most studies focusing on homogeneous solutions. However, in order to develop devices for light-driven water splitting, catalysts need to be translated to metal-oxide surfaces, emphasizing the importance of research in this area.
Article
Chemistry, Multidisciplinary
Felix Herold, Stefan Prosch, Niklas Oefner, Kai Brunnengraeber, Oliver Leubner, Yannick Hermans, Kathrin Hofmann, Alfons Drochner, Jan P. Hofmann, Wei Qi, Bastian J. M. Etzold
Summary: A new synthesis strategy utilizing non-nano carbon materials as dehydrogenation catalysts has been developed, allowing for control over macroscopic shape, texture, and crystallinity. By fine-tuning the synthesis, high selectivity active carbon catalysts similar to carbon nanotubes can be obtained, with significantly higher space-time yields in test reactions. This new class of carbon materials is technically scalable, reproducible, and exhibits spherical particles for easy handling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Xiaowei Li, Yan Zhao
Summary: This study reports the use of molecularly imprinted nanoparticles as catalysts that utilize their environmental chirality to control the stereochemical outcomes. The catalytic reactions conducted in water at room temperature show high yields and excellent enantioselectivity.
JOURNAL OF CATALYSIS
(2022)
Review
Chemistry, Physical
Lei Wang
Summary: Artificial photosynthesis plays a significant role in energy conversion and environmental pollutant treatment. Metal-based complexes, as excellent photocatalysis photosensitizers, are highlighted in this review. The evaluation parameters for photosensitizers are summarized and the recent developments in molecular photosensitizers based on transition metal complexes are presented.
Article
Multidisciplinary Sciences
Jie Zhou, Jie Li, Liang Kan, Lei Zhang, Qing Huang, Yong Yan, Yifa Chen, Jiang Liu, Shun-Li Li, Ya-Qian Lan
Summary: This study reports the development of a crystalline hetero-metallic cluster catalyst, MCOF-Ti6Cu3, based on the cooperation between MOF and COF. The catalyst exhibits efficient coupling of photocatalytic CO2 reduction and H2O oxidation by utilizing dynamic covalent bonds between clusters to promote photo-induced charge separation and transfer. The MCOF-Ti6Cu3 catalyst shows fine activity in the conversion of CO2 and water into HCOOH.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Frances A. Houle, Junko Yano, Joel W. Ager
Summary: Single catalysts cannot selectively convert CO2 into complex reduced products. Using multiple catalysts organized into a cascade can provide a channel for the reduction of CO and similar intermediates and generate complex chemicals with improved specificity. However, the rules for selecting catalysts and designing systems with high chemical control are unknown. Efficiency and selectivity of individual catalysts can be optimized, but the overall efficiency of the system depends on managing the timings of chemical steps and transport between catalysts. This Perspective explores the challenges and examines control exerted in natural photosynthetic systems to offer insights for artificial photosynthesis.
Editorial Material
Multidisciplinary Sciences
Sylvain Brimaud
Summary: Certain cancers can lead to weakness and wasting in patients. A mouse model has shown that tumors can block molecules that protect muscle innervation and mass. This discovery may potentially lead to new therapies for this deadly condition.
Review
Chemistry, Physical
Young Hyun Hong, Yong-Min Lee, Wonwoo Nam, Shunichi Fukuzumi
Summary: This review provides an overview of the functional model reactions of photosystem II (PSII) and photosystem I (PSI) for photocatalytic water oxidation and reduction, respectively. The roles of high-valent metal-oxo, -hydroperoxo,-peroxo, and-superoxo complexes as reaction intermediates in photocatalytic water oxidation are discussed, as well as the catalytic mechanisms of water oxidation. The roles of metal hydride complexes in hydrogen evolution and NAD+ reduction to NADH are also explored. The aim is to construct molecular artificial photosynthetic systems that can split water into H2 and O2 in a 2:1 ratio, thus achieving artificial photosynthesis at the molecular level.
Review
Chemistry, Physical
Young Hyun Hong, Yong-Min Lee, Wonwoo Nam, Shunichi Fukuzumi
Summary: Water oxidation in photosystem II (PSII) is catalyzed by Mn4Ca clusters in the oxygen-evolving complex (OEC), involving a manganese(V)oxo species as an active reaction intermediate. Photogenerated charge separation in the PSII photosynthetic reaction center is used to reduce plastoquinone to plastoquinol. In photosystem I (PSI), plastoquinol reduces NADP+ to NADPH via photogenerated charge separation, which serves as a reductant for CO2 reduction in the Calvin cycle. Extensive research has been conducted to mimic PSII and PSI for photocatalytic water oxidation and reduction, with a focus on high-valent metal-oxo, -hydroperoxo, -peroxo, and -superoxo intermediates and metal hydride complexes.
Article
Chemistry, Physical
Rafael F. N. Quadrado, Henrique F. V. Vitoria, Daniele C. Ferreira, Klaus Krambrock, Kelly S. Moreira, Thiago A. L. Burgo, Bernardo A. Iglesias, Andre R. Fajardo
Summary: Polymer aerogels were prepared as support materials for cationic porphyrin organocatalysts, and their catalytic activity in the photodegradation of pharmaceuticals was investigated. The CPA-TMPyPMn aerogel demonstrated superior catalytic potential, achieving rapid degradation of the pharmaceuticals and high COD removal rates. Furthermore, the hybrid aerogel showed recyclability.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Review
Chemistry, Physical
Andrea Erigoni, Urbano Diaz
Summary: Organic-inorganic hybrid catalysts, especially those based on silica, have been extensively researched due to their combination of structural stability and versatility. This review focuses on the synthetic tools and chemistry behind the sol-gel syntheses of hybrid catalysts, as well as exemplificative studies on mono- and multi-functional silica-based catalysts with different active sites. Materials obtained through various approaches are compared in terms of properties and catalytic performances, aiming to provide useful information for researchers in the field.
Article
Multidisciplinary Sciences
Xuan Liu, Bo Li, Guanqun Han, Xingwu Liu, Zhi Cao, De-en Jiang, Yujie Sun
Summary: The synthesis of heterocyclic moieties pertaining to biologically active molecules from biomass-based starting compounds is attractive yet underexplored. In this study, an electrocatalytic Achmatowicz reaction for the synthesis of hydropyranones from biomass-derived furfuryl alcohols was reported.
NATURE COMMUNICATIONS
(2021)
Article
Electrochemistry
Peter T. Smith, Bahiru Punja Benke, Lun An, Younghoon Kim, Kimoon Kim, Christopher J. Chang
Summary: The newly developed supramolecular porous organic cage platform shows high efficiency in catalyzing the electrochemical hydrogen evolution reaction from water at neutral pH, exhibiting significant improvement compared to a planar cobalt porphyrin analog and demonstrating excellent catalytic performance in HER.
Article
Chemistry, Multidisciplinary
Murielle F. Delley, Eva M. Nichols, James M. Mayer
Summary: Understanding the effects of applied potentials and electrolyte solution conditions on interfacial proton transfers at electrode surfaces is crucial for electrochemical technologies. Measurements of the applied potential, electrolyte pD, and concentration determined the relative surface populations of acidic and basic forms of molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Rishi G. Agarwal, Scott C. Coste, Benjamin D. Groff, Abigail M. Heuer, Hyunho Noh, Giovanny A. Parada, Catherine F. Wise, Eva M. Nichols, Jeffrey J. Warren, James M. Mayer
Summary: This paper provides an update and revision to a 2010 review on proton-coupled electron transfer (PCET) reagent thermochemistry, correcting systematic errors and presenting updated tables of thermochemical values. It discusses new conclusions and opportunities arising from the assembled data and techniques, emphasizing the importance of updated thermochemical cycles in PCET reactions for calculation and measurement of Gibbs free energies. Additionally, the paper introduces several emerging fields in PCET thermochemistry, highlighting the diversity of research being conducted in this rapidly growing field.
Article
Chemistry, Multidisciplinary
Chuang Han, Guanqun Han, Shukai Yao, Lan Yuan, Xingwu Liu, Zhi Cao, Arun Mannodi-Kanakkithodi, Yujie Sun
Summary: This study introduces a noble metal-free and ultrathin ZnIn2S4 photocatalyst for deuteration reactions using heavy water as the sole deuterium source. By synthesizing defective two-dimensional ZIS nanosheets with surfactant assistance, the performance is significantly enhanced.
Review
Chemistry, Multidisciplinary
Peng Zhai, Yinwen Li, Meng Wang, Jinjia Liu, Zhi Cao, Jie Zhang, Yao Xu, Xingwu Liu, Yong-Wang Li, Qingjun Zhu, Dequan Xiao, Xiao-Dong Wen, Ding Ma
Summary: The development of advanced FTS techniques for industrialization is a research frontier in heterogeneous catalysis due to the nonrenewable nature of coal and uncompetitive market value. This review discusses the pathways for converting syngas to olefins/aromatics, the key factors influencing catalyst functions, and the challenges in improving product selectivity and catalyst stability. The review also introduces the novel photocatalytic form as a new reaction system and explores the potential industrialization for FTO/FTA.
Article
Chemistry, Physical
Murielle F. Delley, Eva M. Nichols, James M. Mayer
Summary: The identity of electrolyte cations and the applied potential can significantly affect the interfacial acidity, electric fields, and SAM heterogeneity. Large cations such as tetrabutylammonium (TBA+) exhibit stronger electric fields and a more pH-responsive SAM compared to small cations. The insights on electrolyte cation effects are of fundamental interest for various electrochemical applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Multidisciplinary Sciences
Weijun Guo, Junqing Yin, Zhen Xu, Wentao Li, Zhantao Peng, C. J. Weststrate, Xin Yu, Yurong He, Zhi Cao, Xiaodong Wen, Yong Yang, Kai Wu, Yongwang Li, J. W. Niemantsverdriet, Xiong Zhou
Summary: This study provides direct experimental evidence of the ethylene polymerization pathway at the molecular level. Through in situ visualization using scanning tunneling microscopy, it was observed that ethylene polymerization occurs on a specific triangular iron site at the boundary between two carbide domains. In the absence of an activator, a surface-anchored ethylidene serves as the chain initiator and grows through ethylene insertion.
Article
Chemistry, Multidisciplinary
Jeffrey S. Derrick, Matthias Loipersberger, Sepand K. Nistanaki, Aila V. Rothweiler, Martin Head-Gordon, Eva M. Nichols, Christopher J. Chang
Summary: This study investigates the influence of bicarbonate on iron porphyrin-catalyzed electrochemical CO2 reduction and demonstrates that templating bicarbonate near the molecular iron porphyrin catalyst increases its acidity and enhances catalytic rates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Energy & Fuels
Ziyu Zhou, Fan Wang, Tao Yan, Hongliu Wan, Ru Yao, Kun Zhang, Yangping Liu, Shuyuan Wang, Dan Xu, Huaming Hou, Peng He, Yongwang Li, Zhi Cao
Summary: Fischer-Tropsch Synthesis (FTS) is an important method for mass production of long-chain linear alpha-olefins (LAOs), but LAOs are difficult to separate and utilize directly. Epoxidation of LAOs in FTS mixture allows for easier separation, but the reaction itself is challenging. Researchers prepared a Co-Ir composite through pyrolysis of a molecularly defined Co-Ir pair complex, which showed excellent yield in the production of 1,2-epoxydecane.
Article
Chemistry, Multidisciplinary
Lun An, Patricia De La Torre, Peter T. Smith, Mina R. Narouz, Christopher J. Chang
Summary: We present a supramolecular approach to catalyzing photochemical CO2 reduction using second-sphere porosity and charge effects. This work establishes that synergistic pendants in the secondary coordination sphere can be leveraged as a design element to augment catalysis at primary active sites within confined spaces.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Jun Xu, Xingwu Liu, Xingchen Liu, Tao Yan, Hongliu Wan, Zhi Cao, Jeffrey A. Reimer
Summary: This study reports a general method to decipher the apportionment of metal ions in bulk metal-organic frameworks (MOFs) using solid-state nuclear magnetic resonance spectroscopy. The researchers successfully applied this method to Mg1-xNix-MOF-74 and identified all eight possible Mg/Ni arrangements. The results reveal that only two specific Mg/Ni structural arrangements are preferred in Ni-incorporated MOFs.
Editorial Material
Chemistry, Multidisciplinary
Eva M. Nichols
Summary: The electrochemical reduction of phosphate salts shows potential for sustainable production of elemental phosphorus.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Lun An, Mina R. Narouz, Peter T. Smith, Patricia De La Torre, Christopher J. Chang
Summary: A supramolecular strategy integrating two-dimensional cobalt porphyrin units into a three-dimensional porous organic cage architecture was proposed for enhancing the electrochemical nitrate reduction reaction (NO3RR). The resulting structure exhibited improved catalyst stability and activity, leading to a higher turnover frequency of 56 s(-1) for ammonia production. These findings highlight the effectiveness of incorporating 2D molecular units into 3D confined microenvironments for enhancing electrocatalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kaeden Teindl, Brian O. O. Patrick, Eva M. M. Nichols
Summary: This study investigates the contribution of proton transfer driving forces in molecular catalysts for electrochemical CO2 reduction. By synthesizing a series of catalysts with tunable pK(a) and varying acidity of exogenous acids, it is found that the kinetics of catalytic turnover are more sensitive to variations in SCS pK(a) when using more acidic exogenous acids and to variations in exogenous acid pK(a) when SCS acidity is increased.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)