Review
Chemistry, Multidisciplinary
Hongwei Zhang, Xindie Jin, Jong-Min Lee, Xin Wang
Summary: This review discusses the current research status of single atom catalysts (SACS) and outlines five tailoring strategies to improve their electrocatalytic activity, involving optimizing the electronic state of active sites, tuning d orbitals of transition metals, adjusting adsorption strength of intermediates, enhancing electron transfer, and elevating mass transport efficiency. Additionally, the synergistic effect from adjacent atoms and recent advances in tailoring strategies on active sites with binuclear configuration were summarized.
Article
Chemistry, Physical
Chao Ye, Jieqiong Shan, Chongzhi Zhu, Wenjie Xu, Li Song, Yihan Zhu, Yao Zheng, Shi-Zhang Qiao
Summary: Regulating site-to-site interactions between active sites can effectively tailor the electrocatalytic behavior of single-atom catalysts. In this study, a series of interactive Pt SACs with controllable spatial correlation degree and local coordination environment were developed by integrating densely populated Pt single atoms in the sub-lattice of a Co3O4 matrix. These interactive Pt-Co3O4 catalysts demonstrate remarkable electrocatalytic performance toward hydrogen production.
ADVANCED ENERGY MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Songa Choi, Yeji Park, Hee Jin Kim, Sang-Il Choi, Kwangyeol Lee
Summary: Etching is an effective technique to expose catalytically active sites on the surface of nanocrystals. It can enhance catalytic activity and stability by modifying the surface structure and composition. However, there are still challenges in this field that need to be addressed for developing highly stable and active electrocatalysts.
MATERIALS CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Daohao Li, Binbin Wang, Xiaojing Long, Wenjia Xu, Yanzhi Xia, Dongjiang Yang, Xiangdong Yao
Summary: Introducing an asymmetry strategy by designing conjugated polymer catalysts with different degrees of asymmetry can adjust the charge distribution of active centers, leading to improved catalytic activity in the oxygen reduction reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Dongyu Liu, Devan Solanki, Eli Stavitski, Mingtao Li, Shu Hu, Victor S. Batista, Ke R. Yang
Summary: This study demonstrates that alloyed TiO2 electrodes with subsurface redox-active transition metals can enable water oxidation to H2O2 at low overpotentials. The first-row transition metals (Cr, Mn, Fe, and Co) act as reservoirs of oxidizing equivalents that couple to substrate binding sites. The distinct sites for substrate binding and redox state transitions reduce the overpotential of the critical first step of water oxidation and enhance the selectivity for H2O2.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Physical
Rui S. Ribeiro, Ana Luisa S. Vieira, Krzysztof Biernacki, Alexandre L. Magalhaes, Juan J. Delgado, Rafael G. Morais, Natalia Rey-Raap, Raquel P. Rocha, M. Fernando R. Pereira
Summary: Hollow carbon spheres (CSs) were synthesized with stable single-atom Fe-N species as alternatives to noble metals-based electrocatalysts for oxygen reduction reaction (ORR). The CSs were finely tuned through a synthesis methodology requiring only earth-abundant metal precursors. Single-atom Fe-N active sites were introduced on the CSs, resulting in a significant enhancement in ORR activity. Advanced characterization and molecular simulation studies revealed the crucial role of nitrogen in anchoring individual iron atoms and modulating the charge density nearby the active sites.
Article
Chemistry, Physical
Huizhu Cai, Bingbing Chen, Xiao Zhang, Yuchen Deng, Dequan Xiao, Ding Ma, Chuan Shi
Summary: This study synthesized Fe3C/C and Fe2N/C samples, and identified single sites of FeN4 species in the Fe2N/C sample after acid leaching, serving as an ideal model for identification of catalytic functions of single sites of FeN4 in ORR. A correlation was found between the concentration of low spin (FeN4)-N-II species by Mossbauer spectra and the kinetic current density at 0.8 V in alkaline media, confirming the catalytic roles of low spin (FeN4)-N-II species as highly active sites for ORR.
Article
Chemistry, Inorganic & Nuclear
Song-Jeng Huang, Adil Muneeb, Palani Sabhapathy, Anji Sheelam, Khasim Saheb Bayikadi, Raman Sankar
Summary: This study demonstrates that by designing an oxide with specific structure and element doping, the catalytic activity of oxygen reduction and oxygen electrolysis reactions can be improved. It was found that the increase in the number of sites with the Co4+ oxidation state can enhance the catalytic activity of the catalyst. Additionally, the doped Ca fraction can also affect the adsorbed oxygen species, leading to changes in catalytic activity.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Fantao Kong, Yifan Huang, Meixin Chen, Ge Meng, Han Tian, Yafeng Chen, Ziwei Chang, Chang Chen, Wenping Sun, Xiangzhi Cui, Jianlin Shi
Summary: Hierarchical carbon nanocages of Fe-N-C single-atom catalysts (FeSA-N/Cs-OAc) were created using a novel acetate thermolysis-assisted route, resulting in abundant edge-sited Fe-N-4 moieties in well-defined mesoporous channels. The optimized FeSA-N/Cs-OAc catalyst showed excellent oxygen reduction reaction (ORR) activities and demonstrated high performance in zinc-air batteries and fuel cells.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Multidisciplinary
Lei Chen, Chaozheng He, Ran Wang, Qian Li, Jian Zeng, Wei Liu, Yuchao Wang, Qichen Wang, Tong Ye, Yougen Tang, Yongpeng Lei
Summary: Single atom catalysts with well-dispersed metal atoms have distinctive performances for electrocatalysis. The synthesis of Mo single atomic sites and ultrasmall Mo2C/MoN clusters on nitrogen-doped carbon was achieved through pyrolysis of bimetallic metalorganic frameworks. XANES and DFT calculations confirmed the structure and N-2 adsorption capability of Mo-N3C single atoms for electrochemical N-2 reduction.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Muhammad Adib Abdillah Mahbub, Joao R. C. Junqueira, Xin Wang, Jian Zhang, Stefan Dieckhoefer, Sabine Seisel, Debanjan Das, Wolfgang Schuhmann
Summary: A facile strategy of using 2-methyl-imidazole coordinated to Bi to boost CO2 reduction to formate with high selectivity and activity is reported.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Zhisen Li, Xiaojian Wen, Fengjiao Chen, Qiuyue Zhang, Qinghua Zhang, Lin Gu, Jun Cheng, Binghui Wu, Nanfeng Zheng
Summary: This study presents a crystal-phase heterostructured Ni catalyst with high activity and stability for electrocatalytic hydrogen production. The unique surface chemical properties of hexagonal close packing endow the catalyst with excellent performance in H2 evolution, making it a promising alternative to noble metal catalysts.
Article
Engineering, Environmental
Jiani Li, Li-Wei Chen, Yu-Chen Hao, Man Yuan, Jianning Lv, Anwang Dong, Shuai Li, Hongfei Gu, An-Xiang Yin, Wenxing Chen, Pengfei Li, Bo Wang
Summary: Single-atom Pd catalysts with asymmetric coordination environments have been developed and anchored on optimized oxidized mesoporous carbon. The catalyst exhibits high selectivity for CO production and high Faradaic efficiency. Furthermore, the catalyst-based gas diffusion layer shows excellent current density and long-term stability. A rechargeable Zn-CO2 battery is constructed with the optimal gas diffusion electrode, achieving a high power density.
CHEMICAL ENGINEERING JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Samar Batool, Marcel Langer, Stephen Nagaraju Myakala, Magdalena Heiland, Dominik Eder, Carsten Streb, Alexey Cherevan
Summary: This review summarizes prominent examples of thiomolybdate-based electro- and photocatalysis and provides a comprehensive analysis of their reactivities under homogeneous and heterogenized conditions. The study examines the active sites of thiomolybdates relevant for the hydrogen evolution reaction and discusses the shift from solution-phase to surface-supported thiomolybdates with a focus on applications in electrocatalysis and photocatalysis.
ADVANCED MATERIALS
(2023)
Article
Nanoscience & Nanotechnology
Daniel Zambo, Pascal Rusch, Franziska Lubkemann, Nadja C. Bigall
Summary: By optimizing the synthesis of noble-metal nanorods and cryoaerogels, functional macrostructures with prominent electrocatalytic activity can be constructed.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Analytical
Jose M. Gisbert-Gonzalez, William Cheuquepan, Adolfo Ferre-Vilaplana, Enrique Herrero, Juan M. Feliu
Summary: Adsorbed amino acids can modulate the behavior of metal nanoparticles in advanced applications through interactions with surfaces. The adsorption behavior of glutamate on Au(111) surface is influenced by solution pH and surface charge. Glutamate adsorption involves deprotonation of carboxylic groups and bonding in a bidentate configuration. The oxidation of glutamate only occurs on an oxidized surface, involving the transfer of an oxygen group while the main chain remains intact according to FTIR spectra.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2021)
Article
Electrochemistry
Rodolfo M. Antoniassi, Heiki Erikson, Jose Solla-Gullon, Roberto M. Torresi, Juan M. Feliu
Summary: By controlling the shape, metal nanoparticles can be significantly improved for electrocatalysis, but overcoming limitations from large particle size is necessary for practical applications, where nanoparticles should be smaller than 5 nm. Researchers synthesized 3-5 nm cubic Pt nanoparticles with about 40% preferential {100} structure on the surface.
Article
Electrochemistry
Jose M. Gisbert-Gonzalez, Maria V. Oliver-Pardo, Valentin Briega-Martos, Juan M. Feliu, Enrique Herrero
Summary: The behavior of adsorbed CTAB on Au(111) electrodes was studied using electrochemical and FTIR experiments in different aqueous solutions. The results showed that the adsorbed layer was stable in acidic solutions. Changes in electrode charge led to changes in electrode capacitance, resulting in characteristic peaks.
ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Physical
Valentin Briega-Martos, William Cheuquepan, Juan M. Feliu
Summary: In this study, in situ external infrared reflection absorption spectroscopy (IRRAS) was used to detect intermediate species in the ORR mechanism on a flat and well-defined Pt surface. The main ORR-generated intermediate, O-2(-), was identified near the Pt surface in experimental conditions with limited reactivity, allowing for its detection without the use of additional signal enhancement methods.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Review
Chemistry, Physical
Camilo A. Angelucci, Janaina Souza-Garcia, Juan M. Feliu
Summary: The use of single crystal electrodes as model catalysts is widely applied for studying reaction mechanisms. Changes in the surface structure and electronic properties affect adsorption energy, thus impacting catalytic activity. The influence of adsorbed species depends on surface structure, species nature, and the studied reaction.
CURRENT OPINION IN ELECTROCHEMISTRY
(2021)
Article
Electrochemistry
Jose M. Gisbert-Gonzalez, Maria Oliver-Pardo, Francisco J. Sarabia, Victor Climent, Juan M. Feliu, Enrique Herrero
Summary: This study investigated the adsorption behavior of CTAB and CTAOH on gold single crystal electrodes in solutions with different pH values. The stability and composition of the adsorbed adlayer were found to vary with changes in surface charge.
ELECTROCHIMICA ACTA
(2021)
Article
Electrochemistry
R. Martinez-Hincapie, A. Rodes, V Climent, J. M. Feliu
Summary: This study investigates the in-situ spectro-electrochemical behavior of Pt(110) electrodes in contact with acid solutions saturated with CO2, finding potential-dependent signals associated with adsorbed bicarbonate and carbonate anions. The relative intensities of infrared bands at different pH and applied potential values can be used to determine the interfacial pK(a),(2) of CO2. The surface pK(a),(2) value for Pt(110) electrodes is lower than that of Pt(111) electrodes, attributed to differences in surface structure and reactivity.
ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Physical
Ruben Rizo, Juan M. Feliu, Enrique Herrero
Summary: The HPRR on Pt surfaces was studied at pH = 13, showing that Pt(1 1 1) is the most active surface, but its activity decreases with the introduction of steps. Inhibition of HPRR was observed at low potentials, with the onset potential controlled by OHads and the point of maximum entropy. Experiments with different rotation rates suggested the formation of an HPRR intermediate linked to the inhibition process.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Rodolfo M. Antoniassi, Heiki Erikson, Jose Solla-Gullon, Roberto M. Torresi, Juan M. Feliu
Summary: The study demonstrates that deposition of Pd on small supported Pt materials leads to enhanced electrocatalytic activity for formic acid electrooxidation, with lower overpotentials and higher oxidation current densities. The intrinsic activity after Pd decoration is significantly increased, while the oxidation overpotential is shifted to lower values by around 200 mV.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Analytical
Manuel J. S. Farias, Benedicto A. Lima, Germano Tremiliosi-Filho, Enrique Herrero
Summary: This study investigated the electro-oxidation of CO in acid media using voltammetric techniques. The results showed that the content of dissolved CO in the solution determined the magnitude and shape of the CO pre-oxidation curve, affecting the electrochemical behavior of CO. The presence of CO traces in the bulk of the solution influenced the diffusion-limited electro-oxidation of CO at active sites.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Andrea Auer, Francisco J. Sarabia, Daniel Winkler, Christoph Griesser, Victor Climent, Juan M. Feliu, Julia Kunze-Liebhaeuser
Summary: It was found that Cu(111) modified with 0.1 and 0.2 monolayers of Ni(OH)(2) exhibits a non-linear activity trend with increasing coverage. In situ structural investigations and studies on the interfacial water orientation revealed a correlation between a specific threshold of surface roughness and the decrease in the ordering of the water network.
Article
Electrochemistry
Madis Lusi, Heiki Erikson, Kaido Tammeveski, Alexey Treshchalov, Arvo Kikas, Helle-Mai Piirsoo, Vambola Kisand, Aile Tamm, Jaan Aruvali, Jose Solla-Gullon, Juan M. Feliu
Summary: The study evaluated three mesoporous nitrogen-doped carbon support materials for oxygen reduction reaction, compared to Vulcan carbon, in 0.1 M KOH and 0.5 M H2SO4 solutions. Palladium nanoparticles were synthesised using the citrate method and the average particle size was determined. The unique porosities of the ECS were evaluated using the BET method, showing similar microporosity but varying mesopore distribution.
ELECTROCHIMICA ACTA
(2021)
Article
Electrochemistry
Andrea Auer, Francisco J. Sarabia, Christoph Griesser, Victor Climent, Juan M. Feliu, Julia Kunze-Liebhaeuser
Summary: Modifying Cu(111) electrodes with different foreign metals or metal hydroxides can significantly influence the electrocatalytic activity for the hydrogen evolution reaction, with Ni(OH)2 and Co(OH)2 enhancements and Cd decreases observed.
ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Physical
Luis E. Botello, V. Climent, J. M. Feliu
Summary: This study focuses on the thermodynamic characteristics of the hydrogen underpotential deposition process on Pt(111) in alkaline media, with a specific emphasis on hydrogen adsorption and its impact on hydrogen evolution.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Ariadna Segundo-Aguilar, Linda V. Gonzalez-Gutierrez, Victor Climent Paya, Juan Feliu, German Buitron, Bibiana Cercado
Summary: The study conducted simultaneous dual production of gaseous biofuels in a two-chamber MEC fed with digester effluents, testing different combinations of biomass content and cell voltage to produce biogas and hydrogen simultaneously. The data generated showed the energy efficiency and economic benefits of this system.
SUSTAINABLE ENERGY & FUELS
(2021)