Review
Chemistry, Multidisciplinary
Niklas W. Kinzel, Christophe Werle, Walter Leitner
Summary: The electrocatalytic transformation of carbon dioxide has long been a topic of interest, with recent focus on it as an alternative strategy for CO2 reduction. Studies have increasingly looked at direct electron transfer and molecular transition metal complexes as catalysts. This can lead to the production of C-1 compounds as well as more complex transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Zhengning Fan, Shenhao Chen, Song Zou, Chanjuan Xi
Summary: The carboxylation reaction of allylic alcohols with carbon dioxide is achieved using photoredox/nickel dual catalysis, resulting in exclusively linear acids with good Z/E stereoselectivity. The use of Hantzsch ester as a reductant instead of stoichiometric metallic reductants allows the reaction to be carried out at room temperature with a blue LED light source. Mechanistic studies indicate that the presence of water in the catalytic system is crucial for the success of the reaction, which is likely to proceed through the oxidative addition of the in situ formed allylic hydrogen carbonate.
Article
Chemistry, Physical
Kendra S. Belthle, Harun Tueysuez
Summary: This concept article provides insight into the origins of life and the prebiotic synthesis of organic compounds at submarine hydrothermal vents. It highlights the similarity between geochemical CO2 reduction at these vents and the biochemical acetyl-CoA pathway in autotrophs. Both pathways involve catalytic transformations with transition metals as active centers.
Article
Chemistry, Applied
Marina Godino-Ojer, Sergio Morales-Torres, Francisco J. Maldonado-Hodar, Elena Perez-Mayoral
Summary: Transition metal-carbon aerogels, such as Mo, Fe, Co, or Cu, serve as effective and selective catalysts for the synthesis of quinoxalines 1 from o-phenylenediamine 2 and α-hydroxy ketones 3, presenting a sustainable alternative to other carbon-based catalysts or MOFs. The doping metal phase, which consists of metal oxides or zero-valent metals, along with the metal loading at the carbon aerogel surface, plays a crucial role in determining the reactivity and selectivity of the catalysts. The Mo-500 catalyst exhibits the highest efficiency and selectivity, likely working through the initial oxidation of α-hydroxy ketones followed by condensation-dehydration reactions.
Review
Chemistry, Physical
Xingchen Liu, Jinjia Liu, Yong Yang, Yong-Wang Li, Xiaodong Wen
Summary: The catalytic conversion of carbon-containing resources remains a major challenge during economic growth and energy mix adjustment globally. Developing efficient catalysts for this conversion is a key solution to energy and environmental problems. Understanding the structure-performance relationship of catalytic materials is crucial for catalyst development.
Article
Chemistry, Multidisciplinary
Shuaiqiang Jia, Qinggong Zhu, Haihong Wu, Shitao Han, Mengen Chu, Jianxin Zhai, Xueqing Xing, Wei Xia, Mingyuan He, Buxing Han
Summary: In this study, trimetallic electrocatalysts were prepared using a one-step co-electrodeposition process. Among the catalysts, Cu10La1Cs1 showed outstanding performance for CO2 electroreduction reaction, with high selectivity and current density. Experimental and theoretical studies demonstrated that doping La and Cs into Cu efficiently enhanced the reaction efficiency.
Article
Chemistry, Multidisciplinary
Qiuying Zhu, Yuying Hu, Hongyu Chen, Chen Meng, Yizhu Shang, Chengcheng Hao, Shuxian Wei, Zhaojie Wang, Xiaoqing Lu, Siyuan Liu
Summary: This study proposes a simple method to construct a graphdiyne (GDY) supported Ag-Cu nanocluster as a selective electrocatalyst for producing C2+ products. Compared to Cu/GDY, the Ag-Cu/GDY tandem scheme exhibits superior performance in CO2RR to C2+ products. Theoretical calculations show that CO has a higher adsorption energy on Cu than on Ag, promoting the drift of *CO from Ag to Cu. Additionally, the key C-C coupling reaction of *CO with *COH is more favored on Ag-Cu/GDY, contributing to the formation of C2+ products.
Article
Chemistry, Multidisciplinary
Jaya Bharti, Lingjing Chen, Zhenguo Guo, Lin Cheng, Joel Wellauer, Oliver S. Wenger, Niklas von Wolff, Kai-Chung Lau, Tai-Chu Lau, Gui Chen, Marc Robert
Summary: Visible-light-driven reduction of CO2 to CO and formate was achieved using a copper bisquaterpyridine complex, with the presence of a weak acid and a sensitizer. The reaction showed high selectivity for formate and CO.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Huiyu Zhang, Han Han, Linfei Xiao, Wei Wu
Summary: This study prepared a series of CoMoCx catalysts using ionic liquids as precursors and optimized the efficiency of CO2 hydrogenation to ethanol by adjusting the carburization temperature. The results showed high ethanol selectivity and yield under optimal reaction conditions.
Article
Chemistry, Multidisciplinary
Julia Joekel, Esma Birsen Boydas, Joeel Wellauer, Oliver S. Wenger, Marc Robert, Michael Roemelt, Ulf-Peter Apfel
Summary: The recent study reported the highly efficient photocatalytic CO2 reduction activity of (CuCoII)-Co-I complex, which was synthesized using an asymmetric cryptand {(NNN)-N-S}(m) comprising distinct sulphur- and nitrogen-rich binding sites. Under visible light irradiation, (CuCoII)-Co-I-{(NNN)-N-S}(m) exhibited high efficiency and selectivity for the CO2-to-CO conversion, primarily attributed to the synergistic catalysis between copper and cobalt.
Article
Chemistry, Physical
Narges Manavi, Bin Liu
Summary: In this study, microkinetic models were developed to describe dual-site catalyst systems for dry reforming of methane. These models helped to promote catalytic reactivity and suppress coke formation, offering insights for rational catalyst designs.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Narges Manavi, Bin Liu
Summary: In this study, microkinetic models were developed to describe dual-site catalyst systems that promote catalytic reactivity and suppress coke formation. According to density functional theory calculations, distinct reactivities of Co and Co-Mo2N interfacial sites in the Co-Mo ternary nitride were observed. Microkinetic modeling was used to quantify the enhancement in syngas production, and it was confirmed that Co3Mo3N is the most effective in mitigating coke formation and sustaining high reactivity.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Review
Chemistry, Physical
Sanshuang Gao, Tianran Wei, Jiaqiang Sun, Qian Liu, Dui Ma, Wenxian Liu, Shusheng Zhang, Jun Luo, Xijun Liu
Summary: Rechargeable aqueous Zn-CO2 batteries have great potential in addressing environmental problems and energy crises due to their utilization of CO2 and energy output. Developing efficient and stable CO2 reduction reaction (CO2RR) electrocatalysts is crucial for the advancement of this technology. Atomically dispersed metal-based catalysts (ADMCs), with high atom-utilization efficiency and superior catalytic activity, are being explored as promising candidates for Zn-CO2 batteries. Recent research has focused on the development of ADMCs, including transition metal and non-transition metal sites, and the relationship between active site structures and CO2RR activity/Zn-CO2 battery performance.
Review
Chemistry, Physical
Shengnan Lin, Tingan Zhang
Summary: This paper focuses on the synthetic methods of metal spinel oxides (MSOs) and their applications in adsorption catalysis, magnetic materials, electrodes, and sensors. The modifications and applications of AB2O4 (M > 2, B = Al, Fe, Co, and Mn) MSOs are compared. The advantages and disadvantages of MSO synthetic methods are briefly introduced and discussed. The future development trends and application extensions for MSO syntheses are also discussed.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Multidisciplinary Sciences
Changjiang Hu, Zhiwen Jiang, Qunyan Wu, Shuiyan Cao, Qiuhao Li, Chong Chen, Liyong Yuan, Yunlong Wang, Wenyun Yang, Jinbo Yang, Jing Peng, Weiqun Shi, Maolin Zhai, Mehran Mostafavi, Jun Ma
Summary: The efficient and selective production of CH3OH from CO2 and water using renewable X/gamma-rays or accelerated electrons is challenging but promising for a carbon-neutral economy. In this study, atomic Cu-Ni dual-metal sites embedded in a metal-organic framework are shown to enable efficient CH3OH production (around 98%) over multiple irradiated cycles. The use of practical electron-beam irradiation and a cost-effective hydroxyl radical scavenger promotes CH3OH production rate to 0.27 mmol g(-1) min(-1). Time-resolved experiments and calculations reveal the direct generation of CO2 center dot-. radical anions via aqueous electrons attachment and cascade hydrogenation steps. This study highlights a radiolytic route for producing CH3OH from CO2 feedstock and introduces a desirable atomic structure to enhance performance.
NATURE COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Physical
Phillip Christopher, Prashant Kamat
ACS ENERGY LETTERS
(2022)
Article
Chemistry, Physical
Emily Schroeder, Phillip Christopher
ACS ENERGY LETTERS
(2022)
Article
Chemistry, Physical
Laura A. Gomez, Reda Bababrik, Mallikharjuna R. Komarneni, Justin Marlowe, Taha Salavati-fard, Andrew D. D'Amico, Bin Wang, Phillip Christopher, Steven P. Crossley
Summary: Selective activation of renewable carboxylic acids on promoted molybdenum oxides to form alcohols and aldehydes is reported in this study. Addition of a very small loading of Pt significantly enhances rates of selective deoxygenation at lower temperatures but diminishes rates at elevated temperatures due to over-reduction of the support. Moreover, incorporation of Pt clusters on MoO3 decreases the apparent activation barrier for acid conversion and highlights the significant role of site regeneration facilitated by hydrogen splitting and spillover.
Editorial Material
Chemistry, Physical
Prashant Kamat, Phillip Christopher
ACS ENERGY LETTERS
(2022)
Letter
Chemistry, Physical
Hossein Robatjazi, Andrea Schirato, Alessandro Alabastri, Phillip Christopher, Emily A. Carter, Peter Nordlander, Naomi J. Halas
Article
Chemistry, Physical
Alex C. Schilling, Nisa Ulumuddin, Volkan Cinar, Ryan T. Hannagan, Kyle Groden, Yicheng Wang, Laura A. Cramer, Paul L. Kress, Dipna A. Patel, Beverly Vo, Adrian Hunt, Phillip Christopher, Iradwikanari Waluyo, Jean-Sabin McEwen, E. Charles H. Sykes
Summary: This study investigates the behavior of Rh single atoms and small clusters on the 29 Cu2O thin film using a surface science approach. Unlike Pt, Rh atoms and clusters coexist and enable low-temperature CO oxidation through different pathways. DFT calculations quantify the energetics of these pathways, while STM and XPS experiments confirm the findings.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Chithra Asokan, Mingjie Xu, Sheng Dai, Xiaoqing Pan, Phillip Christopher
Summary: Synthesizing atomically dispersed Rh species on oxide supports is challenging but achievable through strong electrostatic adsorption, and their characterization can be done using CO probe molecule infrared spectroscopy. This method contributes to the study of structure-function relationships in catalytic reactions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Jun Hee Jang, Jack T. Hopper, Insoo Ro, Phillip Christopher, Mahdi M. Abu-Omar
Summary: The study presents a one-step conversion of bioderived mucic acid to adipates using a heterogeneous, bifunctional Ir-ReOx/C catalyst. The catalyst with low Ir content enables reuse and regeneration for multiple cycles, providing a cost-effective option for the tandem deoxydehydration (DODH)-catalytic transfer hydrogenation (CTH) process. The reported system generates adipates in good yield without the need for additives or high pressure H-2, offering a sustainable and affordable route to manufacturing nylon and other polymers.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Zhexi Lin, Siddharth Deshpande, Steven R. Denny, William N. Porter, Cong Wang, Justin Marlowe, Phillip Christopher, Weiqing Zheng, Stavros Caratzoulas, Dionisios G. Vlachos, Jingguang G. Chen
Summary: This study investigates the reaction mechanism and active sites of THFA ring-opening on a WOx/Pt inverse oxide catalyst using model surface experiments, first-principles calculations, and catalyst characterization. The results demonstrate that the introduction of WOx can modulate the interaction strength between THFA and the surface, facilitating the desorption of the desired product. This study provides insights into catalyst design for the selective ring-opening of biomass-derived oxygenates.
Article
Chemistry, Physical
Gregory Zakem, Phillip Christopher
Summary: The study investigates the effect of active site mobility on reaction kinetics in heterogeneous catalysis. The researchers modified the mobility of atomically dispersed Rhodium on gamma-Al2O3 support and found that restricting mobility leads to lower desorption temperature and higher turnover frequency for a specific reaction. The analysis suggests that the changes in apparent activation entropy are responsible for the promoted rates. The study highlights the importance of active site entropy and controlling it for improving catalytic performance.
Article
Chemistry, Physical
Jordan Finzel, Kenzie M. Sanroman Gutierrez, Adam S. Hoffman, Joaquin Resasco, Phillip Christopher, Simon R. Bare
Summary: Single-atom catalysts (SACs) consisting of dispersed metal atoms have unique reactivity and efficient use of precious metals. X-ray absorption spectroscopy (XAS) is often used to identify metal species, but its limitations in detecting metal clusters have not been critically assessed. This article quantitatively assesses the detection limits of XAS and proposes a screening method using wavelet transform to differentiate atomically dispersed metal species and metal oxide clusters. The study provides best practices for studying SACs with XAS and emphasizes the importance of rigorous characterization.
Article
Chemistry, Multidisciplinary
Baoyuan Liu, Zach Westman, Kelsey Richardson, Dingyuan Lim, Alan L. Stottlemyer, Thomas Farmer, Paul Gillis, Vojtech Vlcek, Phillip Christopher, Mahdi M. Abu -Omar
Summary: Polyurethane (PU) is a widely used plastic, with production reaching 24 million metric tons in 2018 and continuing to grow annually at 4%. However, the accumulation of PU waste poses a challenge for recycling due to its complex composition. Chemical recycling methods offer a potential solution, but there is a lack of understanding and commercial implementation of these methods. This article provides an overview of closed-loop chemical recycling methods for PU waste, focusing on the production of recycled polyol (repolyol) as a substitute for virgin polyol.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Editorial Material
Chemistry, Physical
Phillip Christopher
ACS ENERGY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Jaeha Lee, Peter Tieu, Jordan Finzel, Wenjie Zang, Xingxu Yan, George Graham, Xiaoqing Pan, Phillip Christopher
Summary: The addition of platinum-group metals (PGMs, e.g., Pt) to CeO2 promotes the rate of redox surface reactions in heterogeneous catalysis. However, the mechanistic picture of PGM-promoted H-2 reactions on CeO2 surfaces in powder catalysts remains unclear. This study investigates the influence of Pt nanoclusters and single atoms on H-2 reactions on Pt/CeO2 powder catalysts using controlled catalyst synthesis and various experimental techniques. The results show that Pt can promote H-2 consumption rates even when existing on a small fraction of CeO2 particles, and Pt changes the activation mechanism and rate limiting step for H-2 on CeO2 surfaces.
Article
Engineering, Chemical
Emily K. Schroeder, Prasanna Dasari, Muhammad Amtiaz Nadeem, Dustin Fickel, Phillip Christopher
Summary: The activity and stability of bimetallic Pt-Ir nanoparticles supported on an Al2O3/ZSM-5 mixture were investigated for butane hydrogenolysis to ethane. A specific regeneration protocol involving the exposure of the oxidized catalyst to a butane and hydrogen mixture followed by post-reduction was identified to recover the catalyst activity and enhance its stability. Carefully designed pretreatment protocols that deposit stable adsorbates are presented as a valuable tool for controlling the surface composition of bimetallic nanoparticles and improving their catalytic performance.
ACS ENGINEERING AU
(2023)
