Converting carbon dioxide (CO2) into value-added chemicals is considered as a promising strategy to mitigate climate change. Among the various CO2 reduction techniques, electrochemical CO2 reduction (ERCO2) using renewable energy sources holds significant potential. Consequently, the design and development of electrocatalysts capable of offering both high performance and cost-effectiveness hold the potential to expedite reaction kinetics and facilitate widespread industrial adoption. In recent years, abundant copper sulfide (Cu/S)-associated nanomaterials among various metal-chalcogenides have been of extensive research interest due to their semiconductor and low toxicity properties, enabling them to be used in widespread applications of the ERCO2 field. This review highlights the progress of engineered Cu/S-associated nanomaterials for ERCO2 reactions and elaborates on the correlations of engineering strategies, catalytic activity, and reaction pathways. The paper also summarises the controllable synthesis methods for fabricating various state-of-the-art Cu/S-associated structures and outlines their possible implementation for CO2 reduction as an electrocatalyst. Finally, challenges and prospects are presented for the future development and practical application of Cu/S-associated catalysts for ECO2R to value-added chemicals.
{"title":"Controlled Synthesis of Copper Sulfide-associated Catalysts for Electrochemical Reduction of CO2 to Formic Acid and Beyond: A Review","authors":"Anirban Mukherjee, Maryam Abdinejad, Susanta Sinha Mahapatra, Bidhan Chandra Ruidas","doi":"10.1039/d4ya00302k","DOIUrl":"https://doi.org/10.1039/d4ya00302k","url":null,"abstract":"Converting carbon dioxide (CO2) into value-added chemicals is considered as a promising strategy to mitigate climate change. Among the various CO2 reduction techniques, electrochemical CO2 reduction (ERCO2) using renewable energy sources holds significant potential. Consequently, the design and development of electrocatalysts capable of offering both high performance and cost-effectiveness hold the potential to expedite reaction kinetics and facilitate widespread industrial adoption. In recent years, abundant copper sulfide (Cu/S)-associated nanomaterials among various metal-chalcogenides have been of extensive research interest due to their semiconductor and low toxicity properties, enabling them to be used in widespread applications of the ERCO2 field. This review highlights the progress of engineered Cu/S-associated nanomaterials for ERCO2 reactions and elaborates on the correlations of engineering strategies, catalytic activity, and reaction pathways. The paper also summarises the controllable synthesis methods for fabricating various state-of-the-art Cu/S-associated structures and outlines their possible implementation for CO2 reduction as an electrocatalyst. Finally, challenges and prospects are presented for the future development and practical application of Cu/S-associated catalysts for ECO2R to value-added chemicals.","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zülal Muganlı, İsmail Bütün, Ghazaleh Gharib, Ali Koşar
New-generation sustainable energy systems serve as major tools to mitigate the greenhouse gas emissions and effects of climate change. Biophotovoltaics (BPVs) presents an eco-friendly approach by employing solar energy to ensure self-sustainable bioelectricity. In contrast to other microbial fuel cells (MFCs), carbon feedstock is not essential for generating electricity with BPVs. However, the low power outputs (μW cm−2) obtained from the current systems limit their practical applications. In this study, a new generation polydimethylsiloxane (PDMS) based BPV cell unit was developed with a 3D hydrogel scaffold-based bio-anode to enable microbial biofilm formation for substantial electron capture and extracellular electron transfer. Moreover, the fabricated device was supported using an air-cathode electrode to elevate the gas exchange, thereby enabling optimum photosynthesis. Synechocystis sp. PCC 6803 seeded the 3D bio-anode embedded BPV cell, whose electrical characteristics were analyzed under the illumination of white light as day/night cycles with continuous feeding by the microchannel. For the first five days, the results indicated that the maximum power densities were 0.0534 W m−2 for dark hours and 0.03911 W m−2 for light hours without causing any effect on the cellular morphology of the cyanobacteria. As a result, the developed hydrogel scaffold-based bio-anode embedded BPV cell led to higher power densities via enabling a simple, self-sustainable, biocompatible, and eco-friendly energy harvesting platform with a possible capability in the applications of power lab-on-a-chip (LOC), point-of-care (POC), and small-scale portable electronic devices.
新一代可持续能源系统是减缓温室气体排放和气候变化影响的主要工具。生物光电（BPV）是一种生态友好型方法，它利用太阳能确保生物电力的自我可持续性。与其他微生物燃料电池（MFCs）相比，生物光伏发电不需要碳原料。然而，现有系统的低功率输出（μW cm-2）限制了其实际应用。本研究开发了一种基于聚二甲基硅氧烷（PDMS）的新一代 BPV 单元，该单元采用三维水凝胶支架生物阳极，可形成微生物生物膜，从而实现大量电子捕获和细胞外电子传递。此外，还利用空气阴极电极支持所制造的装置，以提高气体交换，从而实现最佳光合作用。将 Synechocystis sp. PCC 6803 作为三维生物阳极嵌入式 BPV 细胞的种子，在白光的昼夜循环照射下，通过微通道持续进水，对其电学特性进行了分析。结果表明，在最初的五天中，暗时的最大功率密度为 0.0534 W m-2，亮时的最大功率密度为 0.03911 W m-2，但并未对蓝藻的细胞形态造成任何影响。因此，所开发的基于水凝胶支架的生物阳极嵌入式 BPV 电池可实现更高的功率密度，是一种简单、可自我维持、生物兼容和生态友好的能量收集平台，可应用于功率实验室芯片（LOC）、护理点（POC）和小型便携式电子设备。
{"title":"Electricity generation using a microbial 3D bio-anode embedded bio-photovoltaic cell in a microfluidic chamber","authors":"Zülal Muganlı, İsmail Bütün, Ghazaleh Gharib, Ali Koşar","doi":"10.1039/d4ya00278d","DOIUrl":"https://doi.org/10.1039/d4ya00278d","url":null,"abstract":"New-generation sustainable energy systems serve as major tools to mitigate the greenhouse gas emissions and effects of climate change. Biophotovoltaics (BPVs) presents an eco-friendly approach by employing solar energy to ensure self-sustainable bioelectricity. In contrast to other microbial fuel cells (MFCs), carbon feedstock is not essential for generating electricity with BPVs. However, the low power outputs (μW cm<small><sup>−2</sup></small>) obtained from the current systems limit their practical applications. In this study, a new generation polydimethylsiloxane (PDMS) based BPV cell unit was developed with a 3D hydrogel scaffold-based bio-anode to enable microbial biofilm formation for substantial electron capture and extracellular electron transfer. Moreover, the fabricated device was supported using an air-cathode electrode to elevate the gas exchange, thereby enabling optimum photosynthesis. <em>Synechocystis</em> sp. PCC 6803 seeded the 3D bio-anode embedded BPV cell, whose electrical characteristics were analyzed under the illumination of white light as day/night cycles with continuous feeding by the microchannel. For the first five days, the results indicated that the maximum power densities were 0.0534 W m<small><sup>−2</sup></small> for dark hours and 0.03911 W m<small><sup>−2</sup></small> for light hours without causing any effect on the cellular morphology of the cyanobacteria. As a result, the developed hydrogel scaffold-based bio-anode embedded BPV cell led to higher power densities <em>via</em> enabling a simple, self-sustainable, biocompatible, and eco-friendly energy harvesting platform with a possible capability in the applications of power lab-on-a-chip (LOC), point-of-care (POC), and small-scale portable electronic devices.","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ashil Augustin, Manova Santhosh Yesupatham, M. D. Dhileepan, Sanguk Son, Ezhakudiyan Ravindran, Neppolian Bernaurdshaw, Hyoung-il Kim, Karthikeyan Sekar
The concern regarding energy scarcity and environmental issues is effectively addressed by the photocatalytic hydrogen production. The effective combination among semiconductor materials is capable of preventing the exciton recombination, making it a method that is highly effective for enhancing photocatalytic activity. In this report, conjugated polymer encapsulated with metal oxide photocatalyst is synthesised using a simple exsitu synthesis method. The encapsulation of polymer with CeO2 nanoparticles results in exceptional performance in H2 production, as the samples exhibit improved visible light absorption and a significant increase in charge transfer efficiency. This is accredited to the high charge transfer and reduced recombination in the composite. The efficient transfer of photogenerated holes has resulted in a substantial decline in the recombination rate of excitons, and the rate of photocatalytic H2 production has been substantially enhanced. The results indicated that the hydrogen evolution of 10 wt.% CeO2/C3N5 composites was 1256 μmol/g/h, whereas C3N5 was 125 μmol/g/h. The electrochemical analysis showed that the optimised composites have low electron hole recombination rate and improved visible light absorption, thereby exhibiting excellent photocatalytic activity. It is noteworthy that the proposed research is the first study to report on the hydrogen evolution via photocatalysis using CeO2/C3N5 composites. Consequently, this research offers a new perspective on the design of organic inorganic heterostructures and will provide a novel pathway to their catalytic capabilities.
{"title":"Construction of organic inorganic hybrid composite derived from C3N5 incorporated with CeO2 for the enhanced photocatalytic hydrogen evolution","authors":"Ashil Augustin, Manova Santhosh Yesupatham, M. D. Dhileepan, Sanguk Son, Ezhakudiyan Ravindran, Neppolian Bernaurdshaw, Hyoung-il Kim, Karthikeyan Sekar","doi":"10.1039/d4ya00476k","DOIUrl":"https://doi.org/10.1039/d4ya00476k","url":null,"abstract":"The concern regarding energy scarcity and environmental issues is effectively addressed by the photocatalytic hydrogen production. The effective combination among semiconductor materials is capable of preventing the exciton recombination, making it a method that is highly effective for enhancing photocatalytic activity. In this report, conjugated polymer encapsulated with metal oxide photocatalyst is synthesised using a simple exsitu synthesis method. The encapsulation of polymer with CeO2 nanoparticles results in exceptional performance in H2 production, as the samples exhibit improved visible light absorption and a significant increase in charge transfer efficiency. This is accredited to the high charge transfer and reduced recombination in the composite. The efficient transfer of photogenerated holes has resulted in a substantial decline in the recombination rate of excitons, and the rate of photocatalytic H2 production has been substantially enhanced. The results indicated that the hydrogen evolution of 10 wt.% CeO2/C3N5 composites was 1256 μmol/g/h, whereas C3N5 was 125 μmol/g/h. The electrochemical analysis showed that the optimised composites have low electron hole recombination rate and improved visible light absorption, thereby exhibiting excellent photocatalytic activity. It is noteworthy that the proposed research is the first study to report on the hydrogen evolution via photocatalysis using CeO2/C3N5 composites. Consequently, this research offers a new perspective on the design of organic inorganic heterostructures and will provide a novel pathway to their catalytic capabilities.","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The hybrid air-volt ammonia cracker (HAVAC) represents a novel approach to centralised ammonia cracking for hydrogen production, enhancing both efficiency and scalability. This novel process integrates renewable electricity and autothermal operation to crack blue or green ammonia, achieving a high thermal efficiency of 94% to 95%. HAVAC demonstrates impressive ammonia conversion rates up to 99.4% and hydrogen yields between 84% and 99.5%, with hydrogen purity of 99.99% meeting ISO 14687:2019 standards. Key innovations include the process's flexibility to operate in three modes: 100% renewable electricity, 100% air autothermal, or a hybrid approach. This versatility optimizes energy use and adapts to varying conditions. The gas heated cracker (GHC) within HAVAC efficiently reduces energy demands by utilizing waste heat. Modelled using the Aspen Plus Simulator and validated against experimental data, HAVAC's economic analysis indicates a levelized cost of hydrogen (LCOH) between $3.80 per kg-H2 and $6.00 per kg-H2. The process's environmental benefits include reduced greenhouse gas emissions and effective NOx waste management. Future research will focus on scaling up, reducing ammonia feed cost, optimizing catalysts, and enhancing waste management. HAVAC offers substantial promise for advancing hydrogen production and supporting a sustainable, carbon-free hydrogen economy. The technical and economic data generated by this analysis will assist decision-makers and researchers in advancing the pursuit of a carbon-free hydrogen economy.
{"title":"Novel carbon-free innovation in centralised ammonia cracking for a sustainable hydrogen economy: the hybrid air-volt ammonia cracker (HAVAC) process","authors":"Chidozie Eluwah, Paul S. Fennell","doi":"10.1039/d4ya00483c","DOIUrl":"https://doi.org/10.1039/d4ya00483c","url":null,"abstract":"The hybrid air-volt ammonia cracker (HAVAC) represents a novel approach to centralised ammonia cracking for hydrogen production, enhancing both efficiency and scalability. This novel process integrates renewable electricity and autothermal operation to crack blue or green ammonia, achieving a high thermal efficiency of 94% to 95%. HAVAC demonstrates impressive ammonia conversion rates up to 99.4% and hydrogen yields between 84% and 99.5%, with hydrogen purity of 99.99% meeting ISO 14687:2019 standards. Key innovations include the process's flexibility to operate in three modes: 100% renewable electricity, 100% air autothermal, or a hybrid approach. This versatility optimizes energy use and adapts to varying conditions. The gas heated cracker (GHC) within HAVAC efficiently reduces energy demands by utilizing waste heat. Modelled using the Aspen Plus Simulator and validated against experimental data, HAVAC's economic analysis indicates a levelized cost of hydrogen (LCOH) between $3.80 per kg-H<small><sub>2</sub></small> and $6.00 per kg-H<small><sub>2</sub></small>. The process's environmental benefits include reduced greenhouse gas emissions and effective NOx waste management. Future research will focus on scaling up, reducing ammonia feed cost, optimizing catalysts, and enhancing waste management. HAVAC offers substantial promise for advancing hydrogen production and supporting a sustainable, carbon-free hydrogen economy. The technical and economic data generated by this analysis will assist decision-makers and researchers in advancing the pursuit of a carbon-free hydrogen economy.","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rocío Sayago-Carro, Luis J Jinénez-Chavarriga, Esperanza Fernández-García, Anna Kubacka, Marcos Fernández-García
Hydrogen generation through a photocatalytic process appears a promising technology to produce this energy vector through a novel, efficient, green, and sustainable process. The fruitful use of sunlight as excitation source and renewable bio-derived reactants as well as the development of highly efficient catalysts are required to achieve this goal. In this perspective article, we focus on describing how to braid energy and sustainability sides of the hydrogen photo-generation into a single parameter, allowing quantitative measurement and trustful comparison of different catalytic systems. Starting from the energy-related efficiency parameters defined by the IUPAC, we present novel approaches leading to parameters enclosing energy and sustainability information. The study is completed with the analysis of other, non-IUPAC, parameters of broad use such as the Solar-to-Hydrogen observable. To set of results available in the literature for the water splitting reaction and the use of bio-derived sacrificial molecules is reviewed to assess the potential of such reactions in the energy-efficient and sustainable production of hydrogen.
{"title":"Efficiency in Photocatalytic Production of Hydrogen: Energetic and Sustainability implications","authors":"Rocío Sayago-Carro, Luis J Jinénez-Chavarriga, Esperanza Fernández-García, Anna Kubacka, Marcos Fernández-García","doi":"10.1039/d4ya00361f","DOIUrl":"https://doi.org/10.1039/d4ya00361f","url":null,"abstract":"Hydrogen generation through a photocatalytic process appears a promising technology to produce this energy vector through a novel, efficient, green, and sustainable process. The fruitful use of sunlight as excitation source and renewable bio-derived reactants as well as the development of highly efficient catalysts are required to achieve this goal. In this perspective article, we focus on describing how to braid energy and sustainability sides of the hydrogen photo-generation into a single parameter, allowing quantitative measurement and trustful comparison of different catalytic systems. Starting from the energy-related efficiency parameters defined by the IUPAC, we present novel approaches leading to parameters enclosing energy and sustainability information. The study is completed with the analysis of other, non-IUPAC, parameters of broad use such as the Solar-to-Hydrogen observable. To set of results available in the literature for the water splitting reaction and the use of bio-derived sacrificial molecules is reviewed to assess the potential of such reactions in the energy-efficient and sustainable production of hydrogen.","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Correction for ‘Acid–base concentration swing for direct air capture of carbon dioxide’ by Anatoly Rinberg and Michael J. Aziz, Energy Adv., 2024, https://doi.org/10.1039/d4ya00251b.
对 Anatoly Rinberg 和 Michael J. Aziz 的 "直接空气捕获二氧化碳的酸碱浓度摆动 "的更正，《能源进展》，2024 年，https://doi.org/10.1039/d4ya00251b。
{"title":"Correction: Acid–base concentration swing for direct air capture of carbon dioxide","authors":"Anatoly Rinberg and Michael J. Aziz","doi":"10.1039/D4YA90035A","DOIUrl":"https://doi.org/10.1039/D4YA90035A","url":null,"abstract":"<p >Correction for ‘Acid–base concentration swing for direct air capture of carbon dioxide’ by Anatoly Rinberg and Michael J. Aziz, <em>Energy Adv.</em>, 2024, https://doi.org/10.1039/d4ya00251b.</p>","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ya/d4ya90035a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142174073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tiago Fernandes, Ramsundar Rani Mohan, Laura Donk, Wei Chen, Chiara Biz, Mauro Fianchini, Saeed Kamali, Siavash Mohammad Alizadeh, Anna Kitayev, Aviv Ashdot, Miles Page, Laura M. Salonen, Sebastian Kopp, Ervin Tal Gutelmacher, José Gracia, Marta Costa Figueiredo, Yury V. Kolen’ko
The oxygen evolution reaction (OER) is usually the bottleneck in water electrolysis due to its sluggish kinetics, resulting in increased costs in the production of green hydrogen. Therefore, there is a need for more efficient, stable, and ideally, critical-raw-material-free catalysts. To this end, we have synthesized nanosized spinel ferrites CoFe2O4, NiFe2O4, and ZnFe2O4, and a high-entropy spinel ferrite Zn0.2Mn0.2Ni0.2Co0.2Fe2.2O4 through a simple coprecipitation reaction in an automated reactor on a gram scale. The powder X-ray diffraction and transmission electron microscopy studies revealed crystallite sizes of 20–35 nm. Insight into the oxidation states and cation distribution in the mixed spinel systems was gained through X-ray photoelectron and Mössbauer spectroscopy studies. The activity of all spinel ferrites was tested for the OER through half-cell laboratory measurements and full-cell anion exchange membrane electrolysis (AEMEL), where Zn0.2Mn0.2Ni0.2Co0.2Fe2.2O4 showed the lowest overpotential of 432 mV at a current density of 10 mA cm−2. All the synthesized ferrites demonstrated good stability up to 20 h, with NiFe2O4 being the most active in high current density experiments up to 2 A cm−2. In addition, studies on the magnetic properties at room temperature revealed a largely superparamagnetic response of the prepared materials, indicating that quantum spin-exchange interactions facilitate oxygen electrochemistry. Computational calculations shed light on the superior catalytic activities of NiFe2O4 and Zn0.2Mn0.2Ni0.2Co0.2Fe2.2O4, the two strongly correlated oxides that exhibit the highest magnetization and the smallest band gaps, corroborating the recent principles determining the activity of magnetic oxides in electron transfer reactions.
氧进化反应（OER）通常是水电解过程中的瓶颈，因为其动力学反应缓慢，导致生产绿色氢气的成本增加。因此，需要更高效、更稳定、更理想的无临界原料催化剂。为此，我们在克级自动反应器中通过简单的共沉淀反应合成了纳米级尖晶铁氧体 CoFe2O4、NiFe2O4 和 ZnFe2O4 以及高熵尖晶铁氧体 Zn0.2Mn0.2Ni0.2Co0.2Fe2.2O4。粉末 X 射线衍射和透射电子显微镜研究显示结晶尺寸为 20-35 纳米。通过 X 射线光电子学和莫斯鲍尔光谱研究，深入了解了混合尖晶石体系中的氧化态和阳离子分布。通过半电池实验室测量和全电池阴离子交换膜电解 (AEMEL) 测试了所有尖晶石铁氧体的 OER 活性，其中 Zn0.2Mn0.2Ni0.2Co0.2Fe2.2O4 在电流密度为 10 mA cm-2 时的过电位最低，为 432 mV。所有合成的铁氧体在 20 小时内都表现出良好的稳定性，其中 NiFe2O4 在高达 2 A cm-2 的高电流密度实验中最为活跃。此外，对室温下磁性能的研究表明，所制备的材料在很大程度上具有超顺磁性，这表明量子自旋交换相互作用促进了氧的电化学作用。计算阐明了 NiFe2O4 和 Zn0.2Mn0.2Ni0.2Co0.2Fe2.2O4（这两种强相关氧化物表现出最高的磁化率和最小的带隙）的卓越催化活性，证实了最近确定磁性氧化物在电子转移反应中的活性的原理。
{"title":"Anion exchange membrane water electrolysis over superparamagnetic ferrites","authors":"Tiago Fernandes, Ramsundar Rani Mohan, Laura Donk, Wei Chen, Chiara Biz, Mauro Fianchini, Saeed Kamali, Siavash Mohammad Alizadeh, Anna Kitayev, Aviv Ashdot, Miles Page, Laura M. Salonen, Sebastian Kopp, Ervin Tal Gutelmacher, José Gracia, Marta Costa Figueiredo, Yury V. Kolen’ko","doi":"10.1039/d4ya00170b","DOIUrl":"https://doi.org/10.1039/d4ya00170b","url":null,"abstract":"The oxygen evolution reaction (OER) is usually the bottleneck in water electrolysis due to its sluggish kinetics, resulting in increased costs in the production of green hydrogen. Therefore, there is a need for more efficient, stable, and ideally, critical-raw-material-free catalysts. To this end, we have synthesized nanosized spinel ferrites CoFe<small><sub>2</sub></small>O<small><sub>4</sub></small>, NiFe<small><sub>2</sub></small>O<small><sub>4</sub></small>, and ZnFe<small><sub>2</sub></small>O<small><sub>4</sub></small>, and a high-entropy spinel ferrite Zn<small><sub>0.2</sub></small>Mn<small><sub>0.2</sub></small>Ni<small><sub>0.2</sub></small>Co<small><sub>0.2</sub></small>Fe<small><sub>2.2</sub></small>O<small><sub>4</sub></small> through a simple coprecipitation reaction in an automated reactor on a gram scale. The powder X-ray diffraction and transmission electron microscopy studies revealed crystallite sizes of 20–35 nm. Insight into the oxidation states and cation distribution in the mixed spinel systems was gained through X-ray photoelectron and Mössbauer spectroscopy studies. The activity of all spinel ferrites was tested for the OER through half-cell laboratory measurements and full-cell anion exchange membrane electrolysis (AEMEL), where Zn<small><sub>0.2</sub></small>Mn<small><sub>0.2</sub></small>Ni<small><sub>0.2</sub></small>Co<small><sub>0.2</sub></small>Fe<small><sub>2.2</sub></small>O<small><sub>4</sub></small> showed the lowest overpotential of 432 mV at a current density of 10 mA cm<small><sup>−2</sup></small>. All the synthesized ferrites demonstrated good stability up to 20 h, with NiFe<small><sub>2</sub></small>O<small><sub>4</sub></small> being the most active in high current density experiments up to 2 A cm<small><sup>−2</sup></small>. In addition, studies on the magnetic properties at room temperature revealed a largely superparamagnetic response of the prepared materials, indicating that quantum spin-exchange interactions facilitate oxygen electrochemistry. Computational calculations shed light on the superior catalytic activities of NiFe<small><sub>2</sub></small>O<small><sub>4</sub></small> and Zn<small><sub>0.2</sub></small>Mn<small><sub>0.2</sub></small>Ni<small><sub>0.2</sub></small>Co<small><sub>0.2</sub></small>Fe<small><sub>2.2</sub></small>O<small><sub>4</sub></small>, the two strongly correlated oxides that exhibit the highest magnetization and the smallest band gaps, corroborating the recent principles determining the activity of magnetic oxides in electron transfer reactions.","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Carolina Castello, Tailor Peruzzolo, Marco Bellini, Maria V. Pagliaro, Francesco Bartoli, Enrico Berretti, Lorenzo Poggini, Emanuela Pitzalis, Claudio Evangelisti, Hamish A. Miller
Fuels can be produced from the electrochemical reduction of industrial waste CO2 (e-fuels) using renewable energy and hence are an attractive option for the storage of renewable energy in a chemical form. The energy stored in the e-Fuel may be recovered on-demand using a direct fuel cell thus completing a carbon neutral cycle. Anion exchange membrane fuel cells (AEMFCs) are versatile devices that can be fed by both a gaseous fuel such as H2 and with liquid fuels (e.g. alcohols, formate, hydrazine, NaBH4). Formate is a molecule that can be easily obtained by the electrochemical reduction of CO2 with high selectivity. Efficient re-transformation of the energy stored in the chemical bonds into electrical energy requires the development of efficient and stable electrocatalysts. Palladium alloy catalysts are highly active under alkaline conditions when Pd is mixed with more oxophilic transition metals. Here we report that enhanced activity and stability can be obtained with Au–Pd alloy nanoparticles when compared to a Pd catalyst. Both catalysts are prepared by a metal vapour synthesis method. We show that the key to enhanced performance is the partial segregation of Au to the NP surface that increases oxophilicity and favours the adsorption and transfer of OH− species to the active Pd sites. This enhanced activity translates to high power densities and performance stability when employed in AEMFCs fed with aqueous potassium formate fuel (Peak power density of 0.14 W cm−2, energy efficiency of 33%, faradaic efficiency of 80%).
{"title":"Direct formate anion exchange membrane fuel cells with a PdAu bimetallic nanoparticle anode electrocatalyst obtained by metal vapor synthesis","authors":"Carolina Castello, Tailor Peruzzolo, Marco Bellini, Maria V. Pagliaro, Francesco Bartoli, Enrico Berretti, Lorenzo Poggini, Emanuela Pitzalis, Claudio Evangelisti, Hamish A. Miller","doi":"10.1039/d4ya00324a","DOIUrl":"https://doi.org/10.1039/d4ya00324a","url":null,"abstract":"Fuels can be produced from the electrochemical reduction of industrial waste CO<small><sub>2</sub></small> (e-fuels) using renewable energy and hence are an attractive option for the storage of renewable energy in a chemical form. The energy stored in the e-Fuel may be recovered on-demand using a direct fuel cell thus completing a carbon neutral cycle. Anion exchange membrane fuel cells (AEMFCs) are versatile devices that can be fed by both a gaseous fuel such as H<small><sub>2</sub></small> and with liquid fuels (<em>e.g.</em> alcohols, formate, hydrazine, NaBH<small><sub>4</sub></small>). Formate is a molecule that can be easily obtained by the electrochemical reduction of CO<small><sub>2</sub></small> with high selectivity. Efficient re-transformation of the energy stored in the chemical bonds into electrical energy requires the development of efficient and stable electrocatalysts. Palladium alloy catalysts are highly active under alkaline conditions when Pd is mixed with more oxophilic transition metals. Here we report that enhanced activity and stability can be obtained with Au–Pd alloy nanoparticles when compared to a Pd catalyst. Both catalysts are prepared by a metal vapour synthesis method. We show that the key to enhanced performance is the partial segregation of Au to the NP surface that increases oxophilicity and favours the adsorption and transfer of OH<small><sup>−</sup></small> species to the active Pd sites. This enhanced activity translates to high power densities and performance stability when employed in AEMFCs fed with aqueous potassium formate fuel (Peak power density of 0.14 W cm<small><sup>−2</sup></small>, energy efficiency of 33%, faradaic efficiency of 80%).","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anton M. Graf, Thomas Cochard, Kiana Amini, Michael S. Emanuel, Shmuel M. Rubinstein, Michael J. Aziz
We introduce operando quantitative electrochemical fluorescence state of charge mapping (QEFSM), a non-invasive technique to study operating electrochemical systems along with a new design of optically transparent microfluidic redox flow cells compatible with the most demanding optical requirements. QEFSM allows quantitative mappings of the concentration of a particular oxidation state of a redox-active species within a porous electrode during its operation. In this study, we used confocal microscopy to map the fluorescence signal of the reduced form of 2,7-anthraquinone disulfonate (AQDS) in a set of multistep-chronoamperometry experiments. Calibrating these images and incorporating an analytical model of quinhydrone heterodimer formation with no free parameters, and accounting for the emission of each species involved, we determined the local molecular concentration and the state of charge (SOC) fields within a commercial porous electrode during operation. With this method, electrochemical conversion and species advection, reaction and diffusion can be monitored at heretofore unprecedented transverse and axial resolution (1 μm and 25 μm, respectively) at frame rates of 0.5 Hz, opening new routes to understanding local electrochemical processes in porous electrodes. We observed pore-scale SOC inhomogeneities appearing when the fraction of electroactive species converted in a single pass through the electrode becomes large.
{"title":"Quantitative local state of charge mapping by operando electrochemical fluorescence microscopy in porous electrodes","authors":"Anton M. Graf, Thomas Cochard, Kiana Amini, Michael S. Emanuel, Shmuel M. Rubinstein, Michael J. Aziz","doi":"10.1039/d4ya00362d","DOIUrl":"https://doi.org/10.1039/d4ya00362d","url":null,"abstract":"We introduce <em>operando</em> quantitative electrochemical fluorescence state of charge mapping (QEFSM), a non-invasive technique to study operating electrochemical systems along with a new design of optically transparent microfluidic redox flow cells compatible with the most demanding optical requirements. QEFSM allows quantitative mappings of the concentration of a particular oxidation state of a redox-active species within a porous electrode during its operation. In this study, we used confocal microscopy to map the fluorescence signal of the reduced form of 2,7-anthraquinone disulfonate (AQDS) in a set of multistep-chronoamperometry experiments. Calibrating these images and incorporating an analytical model of quinhydrone heterodimer formation with no free parameters, and accounting for the emission of each species involved, we determined the local molecular concentration and the state of charge (SOC) fields within a commercial porous electrode during operation. With this method, electrochemical conversion and species advection, reaction and diffusion can be monitored at heretofore unprecedented transverse and axial resolution (1 μm and 25 μm, respectively) at frame rates of 0.5 Hz, opening new routes to understanding local electrochemical processes in porous electrodes. We observed pore-scale SOC inhomogeneities appearing when the fraction of electroactive species converted in a single pass through the electrode becomes large.","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Eun Ju Jeon, Sharif Haidar, Laura Helmers, Arno Kwade, Georg Garnweitner
Polyethylene oxide (PEO)-based polymer electrolytes, despite their cost-effectiveness and ease of processing, suffer from low ionic conductivity at lower temperatures due to the semi-crystalline nature of PEO. Incorporating ceramic filler particles into the polymer matrix offers a potential solution by disrupting its rigid crystalline structure, thereby improving the flexibility of the polymer chains. However, the Li ion conduction pathway within these composite polymer electrolytes (CPEs) remains predominantly within the polymer matrix if the filler particles are only physically mixed. The surface modification of filler particles can improve the interfacial compatibility and ionic conductivity. In this work, two types of filler particles, passive ZrO2 and active Li7La3Zr2O12 (LLZO), are compared and incorporated into PEO–polyethylene glycol (PEG)–lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) CPEs. The surface of the filler particles is functionalized with a silane ligand ((3-glycidyloxypropyl)trimethoxysilane (GPTMS)) prior to their integration into the PEO matrix. This modifies the interfacial properties between the polymer and the filler particles, hence influencing the ionic conductivity. The functionalized ZrO2 fillers enhance the ionic conductivity of the CPEs by reducing the crystallinity of PEO. The PEO–PEG–LiTFSI CPE with 15 vol% of GPTMS–ZrO2 achieved an ionic conductivity of 6.66 × 10−4 S cm−1 at 20 °C, which is significantly higher than that of the standard PEO–LiTFSI (9.26 × 10−6 S cm−1). Additionally, coupling GPTMS to PEO chains without the introduction of filler particles also improved the ionic conductivity, while the incorporation of functionalized LLZO fillers does not, which is attributed to a LiCO3 passivation layer. The results suggest a viable strategy to overcome the inherent limitations of PEO electrolyte, thus offering valuable insights into the design and optimization of CPEs for practical applications.
{"title":"Ion-conductive vs. non-ion-conductive ceramic fillers in silane-linked polyethylene oxide-based composite polymer electrolytes with high room-temperature ionic conductivity","authors":"Eun Ju Jeon, Sharif Haidar, Laura Helmers, Arno Kwade, Georg Garnweitner","doi":"10.1039/d4ya00231h","DOIUrl":"https://doi.org/10.1039/d4ya00231h","url":null,"abstract":"Polyethylene oxide (PEO)-based polymer electrolytes, despite their cost-effectiveness and ease of processing, suffer from low ionic conductivity at lower temperatures due to the semi-crystalline nature of PEO. Incorporating ceramic filler particles into the polymer matrix offers a potential solution by disrupting its rigid crystalline structure, thereby improving the flexibility of the polymer chains. However, the Li ion conduction pathway within these composite polymer electrolytes (CPEs) remains predominantly within the polymer matrix if the filler particles are only physically mixed. The surface modification of filler particles can improve the interfacial compatibility and ionic conductivity. In this work, two types of filler particles, passive ZrO<small><sub>2</sub></small> and active Li<small><sub>7</sub></small>La<small><sub>3</sub></small>Zr<small><sub>2</sub></small>O<small><sub>12</sub></small> (LLZO), are compared and incorporated into PEO–polyethylene glycol (PEG)–lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) CPEs. The surface of the filler particles is functionalized with a silane ligand ((3-glycidyloxypropyl)trimethoxysilane (GPTMS)) prior to their integration into the PEO matrix. This modifies the interfacial properties between the polymer and the filler particles, hence influencing the ionic conductivity. The functionalized ZrO<small><sub>2</sub></small> fillers enhance the ionic conductivity of the CPEs by reducing the crystallinity of PEO. The PEO–PEG–LiTFSI CPE with 15 vol% of GPTMS–ZrO<small><sub>2</sub></small> achieved an ionic conductivity of 6.66 × 10<small><sup>−4</sup></small> S cm<small><sup>−1</sup></small> at 20 °C, which is significantly higher than that of the standard PEO–LiTFSI (9.26 × 10<small><sup>−6</sup></small> S cm<small><sup>−1</sup></small>). Additionally, coupling GPTMS to PEO chains without the introduction of filler particles also improved the ionic conductivity, while the incorporation of functionalized LLZO fillers does not, which is attributed to a LiCO<small><sub>3</sub></small> passivation layer. The results suggest a viable strategy to overcome the inherent limitations of PEO electrolyte, thus offering valuable insights into the design and optimization of CPEs for practical applications.","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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