Carbon Monoxide Tolerant Pt-Based Electrocatalysts for H2-PEMFC Applications: Current Progress and Challenges

The activity degradation of hydrogen-fed proton exchange membrane fuel cells (H2-PEMFCs) in the presence of even trace amounts of carbon monoxide (CO) in the H2 fuel is among the major drawbacks currently hindering their commercialization. Although significant progress has been made, the development of a practical anode electrocatalyst with both high CO tolerance and stability has still not occurred. Currently, efforts are being devoted to Pt-based electrocatalysts, including (i) alloys developed via novel synthesis methods, (ii) Pt combinations with metal oxides, (iii) core–shell structures, and (iv) surface-modified Pt/C catalysts. Additionally, the prospect of substituting the conventional carbon black support with advanced carbonaceous materials or metal oxides and carbides has been widely explored. In the present review, we provide a brief introduction to the fundamental aspects of CO tolerance, followed by a comprehensive presentation and thorough discussion of the recent strategies applied to enhance the CO tolerance and stability of anode electrocatalysts. The aim is to determine the progress made so far, highlight the most promising state-of-the-art CO-tolerant electrocatalysts, and identify the contributions of the novel strategies and the future challenges. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.The authors thankfully acknowledge co-financing from the European Union and Greek national funds through the Operational Program for Competitiveness, Entrepreneurship, and Innovation, under the program RESEARCH-CREATE-INNOVATE (Project code: T1EDK-02442)

Fundamentals and Principles of Solid-State Electrochemical Sensors for High Temperature Gas Detection

The rapid development of science, technology, and engineering in the 21st century has offered a remarkable rise in our living standards. However, at the same time, serious environmental issues have emerged, such as acid rain and the greenhouse effect, which are associated with the ever-increasing need for energy consumption, 85% of which comes from fossil fuels combustion. From this combustion process, except for energy, the main greenhouse gases-carbon dioxide and steam-are produced. Moreover, during industrial processes, many hazardous gases are emitted. For this reason, gas-detecting devices, such as electrochemical gas sensors able to analyze the composition of a target atmosphere in real time, are important for further improving our living quality. Such devices can help address environmental issues and inform us about the presence of dangerous gases. Furthermore, as non-renewable energy sources run out, there is a need for energy saving. By analyzing the composition of combustion emissions of automobiles or industries, combustion processes can be optimized. This review deals with electrochemical gas sensors based on solid oxide electrolytes, which are employed for the detection of hazardous gasses at high temperatures and aggressive environments. The fundamentals, the principle of operation, and the configuration of potentiometric, amperometric, combined (amperometric-potentiometric), and mixed-potential gas sensors are presented. Moreover, the results of previous studies on carbon oxides (COx), nitrogen oxides (NOx), hydrogen (H2), oxygen (O2), ammonia (NH3), and humidity (steam) electrochemical sensors are reported and discussed. Emphasis is given to sensors based on oxygen ion and proton-conducting electrolytes. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.Fotini Tzorbatzoglou, Costas Molochas, and Panagiotis Tsiakaras thankfully acknowledge co-financing from the European Union and Greek national funds through the Operational Program for Competitiveness, Entrepreneurship, and Innovation, under program RESEARCH-CREATE-INNOVATE (Project code: T1EDK-02442)

Nanostructure Engineering of Metal–Organic Derived Frameworks: Cobalt Phosphide Embedded in Carbon Nanotubes as an Efficient Orr Catalyst

Heteroatom doping is considered an efficient strategy when tuning the electronic and structural modulation of catalysts to achieve improved performance towards renewable energy applications. Herein, we synthesized a series of carbon-based hierarchical nanostructures through the controlled pyrolysis of Co-MOF (metal organic framework) precursors followed by in situ phosphidation. Two kinds of catalysts were prepared: metal nanoparticles embedded in carbon nanotubes, and metal nanoparticles dispersed on the carbon surface. The results proved that the metal nanoparticles embedded in carbon nanotubes exhibit enhanced ORR electrocatalytic performance, owed to the enriched catalytic sites and the mass transfer facilitating channels provided by the hierarchical porous structure of the carbon nanotubes. Furthermore, the phosphidation of the metal nanoparticles embedded in carbon nanotubes (P-Co-CNTs) increases the surface area and porosity, resulting in faster electron transfer, greater conductivity, and lower charge transfer resistance towards ORR pathways. The P-Co-CNT catalyst shows a half-wave potential of 0.887 V, a Tafel slope of 67 mV dec−1, and robust stability, which are comparatively better than the precious metal catalyst (Pt/C). Conclusively, this study delivers a novel path for designing multiple crystal phases with improved catalytic performance for energy devices. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.Acknowledgments: S.S.A. Shah is grateful to the higher education commission (HEC) of Pakistan for IPFP funding at the Institute of Chemistry, The Islamia University of Bahawalpur, Pakistan. Furthermore, P. Tsiakaras, A. Brouzgou and C. Molochas thankfully acknowledge the co-financing by the European Union & Greek National funds through the Operational Program Competitiveness, Entrepreneurship, and Innovation, under the call RESEARCH–CREATE–INNOVATE (T1EDK-02442)

Carbon-monoxide-tolerant pt-based electrocatalysts for h2-pemfc applications: Current progress and challenges

The activity degradation of hydrogen-fed proton exchange membrane fuel cells (H2-PEMFCs) in the presence of even trace amounts of carbon monoxide (CO) in the H2 fuel is among the major drawbacks currently hindering their commercialization. Although significant progress has been made, the development of a practical anode electrocatalyst with both high CO tolerance and stability has still not occurred. Currently, efforts are being devoted to Pt-based electrocatalysts, including (i) alloys developed via novel synthesis methods, (ii) Pt combinations with metal oxides, (iii) core–shell structures, and (iv) surface-modified Pt/C catalysts. Additionally, the prospect of substituting the conventional carbon black support with advanced carbonaceous materials or metal oxides and carbides has been widely explored. In the present review, we provide a brief introduction to the fundamental aspects of CO tolerance, followed by a comprehensive presentation and thorough discussion of the recent strategies applied to enhance the CO tolerance and stability of anode electrocatalysts. The aim is to determine the progress made so far, highlight the most promising state-of-the-art CO-tolerant electrocatalysts, and identify the contributions of the novel strategies and the future challenges. © 2021 by the authors. Licensee MDPI, Basel, Switzerland

Fundamentals and principles of solid-state electrochemical sensors for high temperature gas detection

The rapid development of science, technology, and engineering in the 21st century has offered a remarkable rise in our living standards. However, at the same time, serious environmental issues have emerged, such as acid rain and the greenhouse effect, which are associated with the ever-increasing need for energy consumption, 85% of which comes from fossil fuels combustion. From this combustion process, except for energy, the main greenhouse gases-carbon dioxide and steam-are produced. Moreover, during industrial processes, many hazardous gases are emitted. For this reason, gas-detecting devices, such as electrochemical gas sensors able to analyze the composition of a target atmosphere in real time, are important for further improving our living quality. Such devices can help address environmental issues and inform us about the presence of dangerous gases. Furthermore, as non-renewable energy sources run out, there is a need for energy saving. By analyzing the composition of combustion emissions of automobiles or industries, combustion processes can be optimized. This review deals with electrochemical gas sensors based on solid oxide electrolytes, which are employed for the detection of hazardous gasses at high temperatures and aggressive environments. The fundamentals, the principle of operation, and the configuration of potentiometric, amperometric, combined (amperometric-potentiometric), and mixed-potential gas sensors are presented. Moreover, the results of previous studies on carbon oxides (COx), nitrogen oxides (NOx), hydrogen (H2), oxygen (O2), ammonia (NH3), and humidity (steam) electrochemical sensors are reported and discussed. Emphasis is given to sensors based on oxygen ion and proton-conducting electrolytes. © 2021 by the authors. Licensee MDPI, Basel, Switzerland

Brief Review on High-Temperature Electrochemical Hydrogen Sensors

Hydrogen sensors, especially those operating at high temperatures, are essential tools for the emerging hydrogen economy. Monitoring hydrogen under process conditions to control the reactions for detecting confined species is crucial to the safe, widespread use and public acceptance of hydrogen as fuel. Hydrogen sensors must have a sensitivity ranging from traces of hydrogen (parts per million (ppm)) up to levels near the lower explosive limit (LEL = 4% H2 in the air) for safety reasons. Furthermore, they need to operate in cryogenic, ambient, and high-temperature environments. Herein, emphasis is given to hydrogen sensors based on solid oxide electrolytes (operating at high temperatures), in particular oxygen ion and proton conductors. The review is devoted to potentiometric, amperometric, and combined amperometric-potentiometric hydrogen sensors. Experimental results already reported in the international literature are presented and analyzed to reveal the configuration, principle of operation, and the applied solid electrolytes and electrodes of the high-temperature hydrogen sensors. Additionally, an amperometric sensor able to detect hydrogen and steam in atmospheric air through a two-stage procedure is presented and thoroughly discussed. The discussion reveals that high-temperature hydrogen sensors face different challenges in terms of the electrodes and solid electrolytes to be used, depending on the operating principle of each sensor type. © 2022 by the authors

Nanostructure engineering of metal–organic derived frameworks: Cobalt phosphide embedded in carbon nanotubes as an efficient orr catalyst

Heteroatom doping is considered an efficient strategy when tuning the electronic and structural modulation of catalysts to achieve improved performance towards renewable energy applications. Herein, we synthesized a series of carbon-based hierarchical nanostructures through the controlled pyrolysis of Co-MOF (metal organic framework) precursors followed by in situ phosphidation. Two kinds of catalysts were prepared: metal nanoparticles embedded in carbon nanotubes, and metal nanoparticles dispersed on the carbon surface. The results proved that the metal nanoparticles embedded in carbon nanotubes exhibit enhanced ORR electrocatalytic performance, owed to the enriched catalytic sites and the mass transfer facilitating channels provided by the hierarchical porous structure of the carbon nanotubes. Furthermore, the phosphidation of the metal nanoparticles embedded in carbon nanotubes (P-Co-CNTs) increases the surface area and porosity, resulting in faster electron transfer, greater conductivity, and lower charge transfer resistance towards ORR pathways. The P-Co-CNT catalyst shows a half-wave potential of 0.887 V, a Tafel slope of 67 mV dec−1, and robust stability, which are comparatively better than the precious metal catalyst (Pt/C). Conclusively, this study delivers a novel path for designing multiple crystal phases with improved catalytic performance for energy devices. © 2021 by the authors. Licensee MDPI, Basel, Switzerland

Metal oxides for the electrocatalytic reduction of carbon dioxide: Mechanism of active sites, composites, interface and defect engineering strategies

The electrochemical reduction of CO2 into fine chemicals, assisted with renewable energy, is the most instant approach for balancing the atmospheric CO2 level, as well as for storing solar energy as chemical energy. Due to their easy synthesis and good performance, metal oxides are attractive as electrocatalysts for the CO2 reduction reaction (CO2RR). In this review article, we concise the recent advances in the product efficiency of CO2RR for metal oxide electrocatalysts. It is here worth noticing that, overlooking the metal sites of metal oxide-based catalysts, we only considered the M−O (metal–oxygen bond) active sites for discussion. Further, recent strategies, such as advanced morphologies development and interface and vacancy defect engineering, used to improve the CO2RR performance, are also overviewed. By covering the critical role of catalysts (M−O) structure in efficiency and stability, this review also provides some future aspects for the design and development of efficient metal oxide-based electrocatalysts for CO2RR. © 2022 Elsevier B.V