Article
Chemistry, Multidisciplinary
Qiu-Jin Wu, Duan-Hui Si, Pan-Pan Sun, Yu-Liang Dong, Song Zheng, Qian Chen, Shi-Hua Ye, Di Sun, Rong Cao, Yuan-Biao Huang
Summary: We propose an effective strategy to modulate the highest occupied d-orbital in Cu nanoclusters (NCs) by breaking the coordination symmetry of sites, leading to the production of higher-valued hydrocarbons instead of HCOOH/CO in CO2 electroreduction. By designing an atomically well-defined Cu-6 NC with symmetry-broken Cu-S2N1 active sites, we achieved a high Faradaic efficiency of 65.5% for hydrocarbons at -1.4 V versus reversible hydrogen electrode, with a partial current density of -183.4 mA cm(-2). Theoretical calculations demonstrate that the symmetry-broken Cu-S2N1 sites facilitate the generation of key intermediate *COOH, favoring *CO formation and subsequent hydrogenation and/or C-C coupling for hydrocarbon production. This study provides new insights into the design of atomically precise NCs for efficient CO2RR towards high-value products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Electrochemistry
Yue Zhao, Shan Wang, Lin-Jun Zhu, Meng-Jiao Sun, Teng Zhang, Rong Cao
Summary: This study reports a copper complex, Cu(salan)(2), as an efficient CO2 reduction catalyst in basic aqueous media. The complex displayed different catalytic behaviors in nanocrystalline and graphene-supported forms. The results suggest that site-isolation by dispersion of a molecular catalyst is an effective way to increase stability and tune selectivity for CO2RR electrocatalysis.
Article
Chemistry, Physical
Phebe H. van Langevelde, Errikos Kounalis, Lars Killian, Emily C. Monkcom, Daniel L. J. Broere, Dennis G. H. Hetterscheid
Summary: This study reports a dinuclear copper complex inspired by the active site of multicopper oxidases (MCOs), which undergoes a proton-coupled electron transfer pathway during its electrochemical reduction process, resulting in a larger overpotential. The study also reveals the role of metal-metal cooperativity and the constraints of a rigid ligand framework in catalysis, leading to an improved selectivity for the oxygen reduction reaction (ORR) due to better stabilization of reaction intermediates between the copper centers.
Review
Chemistry, Physical
Bianca Ligt, Emiel J. M. Hensen, Marta Costa Figueiredo
Summary: This review article focuses on recent studies that provide important insights into the surfaces and interfaces during carbon dioxide reduction using ex-situ, in-situ, and operando characterization techniques.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hongyu An, Longfei Wu, Laurens D. B. Mandemaker, Shuang Yang, Jim de Ruiter, Jochem H. J. Wijten, Joris C. L. Janssens, Thomas Hartman, Ward van der Stam, Bert M. Weckhuysen
Summary: The study successfully monitored the process of carbon dioxide reduction to hydrocarbons using time-resolved Raman spectroscopy, and found that anodic treatment and surface oxide reduction of the copper electrode can improve CO2RR efficiency and time resolution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Wenwen Lin, Hao Chen, Zihao Li, Kotaro Sasaki, Siyu Yao, Zihao Zhang, Jing Li, Jie Fu
Summary: This study developed a highly efficient heterostructured catalyst, where the interaction between metal and carbon nitride improved electrical conductivity and charge transfer processes, significantly enhancing the selectivity of hydrocarbons in CO2 electroreduction while effectively suppressing H2 evolution.
Article
Multidisciplinary Sciences
Yu Zhang, Long-Zhang Dong, Shan Li, Xin Huang, Jia-Nan Chang, Jian-Hui Wang, Jie Zhou, Shun-Li Li, Ya-Qian Lan
Summary: The study demonstrates that the ECR selectivity depends strongly on the Cu site coordination environment in crystalline porous catalysts, with Cu-DBC showing higher selectivity and activity due to the lower energy barriers of Cu-O-4 sites during the ECR process. This provides a platform for constructing highly selective ECR catalysts with potential applications in the energy conversion field.
NATURE COMMUNICATIONS
(2021)
Article
Environmental Sciences
Min Hong, Qinian Wang, Jun Sun, Chao Wu
Summary: This study reports a novel Cu-based electrode (IE-Cu-400) for the electrochemical reduction of nitrate (NO3-) with improved activity and selectivity compared to traditional Cu-based electrodes. The enhanced performance of IE-Cu-400 is attributed to its smaller particles, high oxidation state of copper (Cu2+ in CuO), increased number of active sites, improved adsorption and reduction ability for NO2-, increased surface area, and high density of grain boundaries. IE-Cu-400 also demonstrates high stability for the electrochemical reduction of nitrate.
SCIENCE OF THE TOTAL ENVIRONMENT
(2022)
Article
Engineering, Environmental
Jian Zhang, Hao Wu, Di Zhang, Lanhe Zhang, Chuntao Zhu
Summary: An efficient and stable ruthenium/agarose/copper foam composite electrode was successfully prepared for the treatment of antibiotic wastewater. The electrode exhibited excellent catalytic effect and high stability. The composite electrode was characterized by SEM, XRD, and XPS, and the results confirmed its properties. The experimental results showed that the electrode achieved a degradation efficiency of 79.12% for doxycycline and demonstrated good reusability and safety.
JOURNAL OF WATER PROCESS ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Jan Vavra, Tzu-Hsien Shen, Dragos Stoian, Vasiliki Tileli, Raffaella Buonsanti
Summary: This study reveals the reconstruction mechanism of Cu-based nanocatalysts during the electrochemical CO2 reduction reaction, as well as the key role of copper oxides in this process, through a combination of electrochemical in situ transmission electron microscopy and operando X-ray absorption spectroscopy. Understanding these underlying processes provides a pathway to rational design of Cu electro(re)deposited catalysts and stability improvement for catalysts fabricated by other methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jingbo Wen, Zixuan Wan, Xiao Hu, Jianlin Huang, Xiongwu Kang
Summary: In this study, mixed copper oxide catalysts were prepared by a hydrothermal method and their structure was modified using electrochemical cycling. The catalytic performance of the modified catalysts towards CO2 reduction was significantly improved, showing high efficiency and current density for two-carbon products in alkaline solution.
JOURNAL OF CO2 UTILIZATION
(2022)
Article
Chemistry, Multidisciplinary
Wahyu Prasetyo Utomo, Hao Wu, Yun Hau Ng
Summary: In this study, the performance of electrocatalytic nitrogen reduction reaction (NRR) is enhanced by loading copper nanoparticles on oxygen-deficient TiO2. Compared to pristine TiO2, the modified catalyst exhibits higher ammonia yield of 13.6 mu g mg(cat)(-1) h(-1) at -0.5 V versus reversible hydrogen electrode (RHE) and Faradaic efficiency of 17.9% at -0.4 V versus RHE. The enhanced performance is attributed to the increased electrochemically active surface area, promoted electron transfer, and strong metal-support interaction (SMSI) between Cu nanoparticles and oxygen-deficient TiO2.
Article
Chemistry, Physical
Benjamin P. Charnay, Zhihao Cui, Melissa A. Marx, Joseph Palazzo, Anne C. Co
Summary: This study investigates the electrochemical reduction of aldehydes to alcohols as a pathway for converting CO2 to alcohols. Experimental results support the proposed mechanism of reducing acetaldehyde and propionaldehyde to ethanol and 1-propanol on a Cu catalyst. Notably, acetaldehyde is selectively reduced to ethanol on Cu, but not on Au, as supported by both experimental observations and DFT calculations.
Article
Chemistry, Physical
Sengeni Anantharaj, Taiki Nagamatsu, Shohei Yamaoka, Mochen Li, Suguru Noda
Summary: Efficient catalysis of methanol electrooxidation in alkaline conditions was achieved using 3d transition metal-based oxides and hydroxides, with copper oxides and hydroxides demonstrating exceptional activity. By utilizing the 3D configuration of a copper foam substrate and the inherent nickel impurity present, the copper oxide/hydroxide catalyst showed outstanding methanol oxidation reaction (MOR) activity, as evidenced by high current densities and excellent stability. The presence of nickel impurity led to intrinsic activity enhancement, showcasing the potential for facile enhancement of Cu-based MOR electrocatalysts.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Yi Li, Weitao Shan, Michael J. Zachman, Maoyu Wang, Sooyeon Hwang, Hassina Tabassum, Juan Yang, Xiaoxuan Yang, Stavros Karakalos, Zhenxing Feng, Guofeng Wang, Gang Wu
Summary: By designing dual-metal active sites, the coordination environments of M-N-C catalysts can be expanded. The Ni-Fe catalyst exhibits the most efficient CO2RR activity and promising stability compared to other combinations. This study provides a new approach to improve the activity and selectivity of the CO2 reduction reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Udishnu Sanyal, Simuck F. Yuk, Katherine Koh, Mal-Soon Lee, Kelsey Stoerzinger, Difan Zhang, Laura C. Meyer, Juan A. Lopez-Ruiz, Abhi Karkamkar, Jamie D. Holladay, Donald M. Camaioni, Manh-Thuong Nguyen, Vassiliki-Alexandra Glezakou, Roger Rousseau, Oliver Y. Gutierrez, Johannes A. Lercher
Summary: The hydrogenation of benzaldehyde to benzyl alcohol is significantly promoted by the presence of polar co-adsorbates like substituted phenols, facilitated by external potential. These co-adsorbates enhance the hydrogenation rate by polarizing the carbonyl group and increasing the likelihood of forming a transition state for H addition, leading to a faster hydrogenation route involving phenol as a conduit for proton addition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Electrochemistry
Juan A. Lopez-Ruiz, Yang Qiu, Evan Andrews, Oliver Y. Gutierrez, Jamie D. Holladay
Summary: The study evaluated the electrocatalytic oxidation reaction on an aqueous stream generated via hydrothermal liquefaction, finding that organic nitrogen and sulfur can be oxidized into nitrates and sulfates, with the main reaction products being short chain volatile hydrocarbons and CO2. This reaction can simultaneously achieve denitrification, valorization of organic compounds, and H(2) generation.
JOURNAL OF APPLIED ELECTROCHEMISTRY
(2021)
Article
Chemistry, Physical
Mengze Xu, Juan A. Lopez-Ruiz, Libor Kovarik, Mark E. Bowden, Stephen D. Davidson, Robert S. Weber, I-Wen Wang, Jianli Hu, Robert A. Dagle
Summary: The size of Ni particles has an impact on the catalytic performance in methane thermocatalytic decomposition, with larger particles leading to the formation of carbon nanotubes and smaller particles resulting in graphitic carbon layers. The formation of graphitic carbon layers blocks access to active sites, causing faster deactivation of the catalyst.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Physical
Sebastian Prodinger, Karoline Kvande, Bjornar Arstad, Elisa Borfecchia, Pablo Beato, Stian Svelle
Summary: In this study, the researchers successfully synthesized Cu-MOR materials with different inclinations for the selective oxidation of methane by varying the relative proportion of aluminum situated near the 8-rings and 12-rings of MOR zeolite. The study confirmed the discrete changes of aluminum within the unit cell through spectroscopic techniques and adsorption experiments, and found that Cu2+ species were the active sites in the selective oxidation of methane.
Article
Chemistry, Physical
Yang Qiu, Juan A. Lopez-Ruiz, Guomin Zhu, Mark H. Engelhard, Oliver Y. Gutierrez, Jamie D. Holladay
Summary: This study reports an electrocatalytic decarboxylation method for the production of paraffins, olefins, and alcohols from valeric acid using RuO2 and Pt nanoparticles as electrode catalysts, providing a greener alternative to thermocatalytic decarboxylation. The turnover frequency of the reaction increases with the size of RuO2 nanoparticles, while the specific activity peaks at around 12 nm. Pt nanoparticles were only active for the oxygen evolution reaction. This work demonstrates the potential of nanostructured materials as anodes for the oxidative upgrading of carboxylic acids.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Engineering, Chemical
Changle Jiang, I-Wen Wang, Xinwei Bai, Sonit Balyan, Brandon Robinson, Jianli Hu, Wenyuan Li, Angela Deibel, Xingbo Liu, Fanxing Li, Luke M. Neal, Jian Dou, Yuan Jiang, Robert Dagle, Juan A. Lopez-Ruiz, George Skoptsov
Summary: Methane catalytic pyrolysis, with both convective thermal heating and microwave-driven irradiative heating, showed enhanced catalytic activity and improved kinetics. The presence of free electrons in the carbon atoms within carbon nanotube (CNT) supported catalysts allowed efficient absorption of microwave energy, resulting in a more energy-efficient process. The research demonstrated the potential of transforming natural gas into clean hydrogen and value-added carbon.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
Article
Chemistry, Physical
Xinwei Sun, Einar Vollestad, Per Martin Rorvik, Sebastian Prodinger, Georgios N. Kalantzopoulos, Athanasios Chatzitakis, Truls Norby
Summary: CeO2 surfaces are crucial in heterogeneous catalysis. This study investigates water adsorption, dissociation, and proton migration on internal surfaces of nanoscopic porous CeO2. The results confirm that the surface is hydrogenated to Ce3+ ions and protons H+ and show that physisorption occurs only at high relative humidities, indicating hydrophobic behavior.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Applied
Karoline Kvande, Sebastian Prodinger, Fabian Schlimpen, Pablo Beato, Patrick Pale, Stefan Chassaing, Stian Svelle
Summary: In this study, a solid-state ion exchange method was used to incorporate Cu-I ions into various zeolites. The Cu-I-zeolites showed reactivity towards methane and were capable of producing methanol even without Bronsted acid sites. However, fine-tuning of the Cu sites is necessary to achieve optimal methane activation.
TOPICS IN CATALYSIS
(2023)
Article
Engineering, Chemical
Karoline Kvande, Moses Mawanga, Sebastian Prodinger, Bjorn Gading Solemsli, Jia Yang, Unni Olsbye, Pablo Beato, Edd Anders Blekkan, Stian Svelle
Summary: By studying the stepwise mechanism of Cu-zeolites for direct methane activation to methanol (MTM), it is possible to achieve high selectivity in methanol production. This study investigates the acidity and nature of Cu-sites in MCM-22, an untested material for MTM, using adsorption/desorption experiments with n-propylamine, NH3, and CH4. The Cu-exchanged zeolites show moderate performance in MTM (approximately 0.10 mol(MeOH)/mol(Cu)), and the results obtained from MCM-22 are used to search for structure-activity relationships by comparing with other zeolite frameworks. CO-adsorption FT-IR spectroscopy experiments reveal the presence of multiple distinct Cu-sites in MCM-22, one of which is likely associated with inactive Cu species. NH3 adsorption/desorption experiments indicate that the number and strength of Bronsted acid sites before Cu exchange are limited, resulting in a low concentration of C-H-activating Cu-oxo species.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Engineering, Environmental
Jinyue Jiang, Juan A. Lopez-Ruiz, Yanhong Bian, Dongya Sun, Yuqing Yan, Xi Chen, Junjie Zhu, Harold D. May, Zhiyong Jason Ren
Summary: This study provides a detailed analysis of the scale-up efforts of microbial electrolysis cells (MECs) and summarizes the key factors to develop the technology further. Various scale-up configurations are compared and evaluated from technical and economic perspectives. The study demonstrates that MECs can be profitable in different market scenarios with or without subsidies.
Article
Chemistry, Multidisciplinary
Karoline Kvande, Sebastian Prodinger, Bjorn Gading Solemsli, Silvia Bordiga, Elisa Borfecchia, Unni Olsbye, Pablo Beato, Stian Svelle
Summary: Cu-zeolites can activate the C-H bond of ethane and produce ethylene with high selectivity at 150 degrees C in a cyclic protocol. The ethylene yield is influenced by both the zeolite topology and Cu content. Ethylene adsorption studies suggest that oligomerization of ethylene occurs over protonic zeolites but not over Cu-zeolites. We propose that this observation is due to the formation of an ethoxy intermediate.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Oliver Y. Gutierrez, Katarzyna Grubel, Jotheeswari Kothandaraman, Juan A. Lopez-Ruiz, Kriston P. Brooks, Mark E. Bowden, Tom Autrey
Summary: Using hydrogen to store energy is crucial for achieving sustainability and addressing climate change. Liquid hydrogen carriers can overcome the challenges of handling molecular hydrogen. The bicarbonate-formate cycle, utilizing formate ions as hydrogen and energy carriers, offers a promising solution. This system combines electrochemical and thermochemical operations and has the potential for CO2 capture and energy storage.
Article
Chemistry, Physical
Mengze Xu, Juan A. Lopez-Ruiz, Nickolas W. Riedel, Robert S. Weber, Mark E. Bowden, Libor Kovarik, Changle Jiang, Jianli Hu, Robert A. Dagle
Summary: Thermocatalytic decomposition (TCD) of methane using NiCu/CNT catalysts was studied for CO2-free hydrogen production and carbon co-product. The catalyst's activity and stability were influenced by the Ni/Cu ratio, metal particle size, and operating temperature. The carbon co-product mainly consisted of multiwalled carbon nanotubes (MWCNTs) with varying morphology depending on the Ni/Cu ratio and reaction temperature.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Sebastian Prodinger, Izar Capel Berdiell, Tomas Cordero-Lanzac, Odd Reidar Bygdnes, Bjorn Gading Solemsli, Karoline Kvande, Bjornar Arstad, Pablo Beato, Unni Olsbye, Stian Svelle
Summary: This study demonstrates for the first time how a single-parameter variation influences the synthesis of Mordenite zeolite, resulting in distinct catalysts. The identity of the cation directly impacts the synthesis mechanism, with potassium cations forming a smaller-port variant compared to the larger-port obtained with sodium cations. The positioning of Al in the zeolite structure is found to be the cause of the differences in port size and subsequent catalytic behavior.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Karoline Kvande, Beatrice Garetto, Gabriele Deplano, Matteo Signorile, Bjorn Gading Solemsli, Sebastian Prodinger, Unni Olsbye, Pablo Beato, Silvia Bordiga, Stian Svelle, Elisa Borfecchia
Summary: This study investigates the dynamic changes of Cu-speciation during light alkane selective oxidation over Cu-mordenite zeolites using temperature-programmed reduction experiments and advanced spectroscopy and data analysis methods. The results reveal multiple CuII and CuI components, and correlations between CuII to CuI reduction, methane consumption, and carbon dioxide production.
Article
Chemistry, Physical
Yifan Sun, Ye Lv, Wei Li, Jinli Zhang, Yan Fu
Summary: In this study, PtRu electrocatalysts were fabricated on carbon paper via cyclic electrodeposition for the electrocatalytic hydrogenation (ECH) of phenol. The Pt3Ru3 catalyst exhibited excellent activity and stability for the conversion of phenol to cyclohexanol at ambient temperature and various current densities. The in situ Raman spectroscopy and kinetic study revealed the hydrogenation mechanism of phenol over Pt3Ru3 in acidic electrolyte, providing an effective electrochemical strategy for the facile construction of durable electrode materials and efficient phenol hydrogenation.
JOURNAL OF CATALYSIS
(2024)
Article
Chemistry, Physical
Amir Shahzad, Khezina Rafiq, Muhammad Zeeshan Abid, Naseem Ahmad Khan, Syed Shoaib Ahmad Shah, Raed H. Althomali, Abdul Rauf, Ejaz Hussain
Summary: Photocatalytic hydrogen production through water splitting is an effective method for meeting future energy demands. In this study, researchers synthesized a 1 % Ag2S/Cu2S co-doped CdZnS catalyst and found that it can produce hydrogen at a higher rate. The co-doping of Ag2S and Cu2S in the CdZnS catalyst showed a synergistic effect, with Ag2S promoting oxidation reactions and Cu2S promoting reduction reactions.
JOURNAL OF CATALYSIS
(2024)
