Antonio José Martín Fernández

Last Name

Martín Fernández

First Name

Antonio José

ORCID

0000-0003-3482-8829

Organisational unit

03871 - Pérez-Ramírez, Javier / Pérez-Ramírez, Javier

Show all metadata

Search Results

Publications 1 - 10 of 17

Chlorine-promoted copper catalysts for CO2 electroreduction into highly reduced products
Zou, Tangsheng; Veenstra, Florentine L.P.; Ibáñez-Alé, Enric; et al. (2023)
Cell Reports Physical Science
Chlorinated copper catalysts have shown promise for electroreduction of carbon dioxide to complex products, but the challenging control of chlorination keeps shaded the potential of chlorine as a selectivity promoter. This work develops a gas-phase chlorination strategy based on exposure to diluted hydrochloric acid at different temperatures to study the effect of chlorine content in copper (II) oxide (CuO), copper (I) oxide (Cu2O), and metallic copper (Cu) foils. Contrary to CuO and Cu, chlorination of Cu2O enhances the formation of highly reduced products (those requiring more than two electron transfers). Faradaic efficiency toward these products (0%–14% at -0.8 V vs. the reversible hydrogen electrode) correlates with the surface chlorine content after reaction (0 to 1.8 atom % chlorine), which is maximized for mild initial chlorination degrees (Cu2O:CuCl∼1). Experimental and computational studies suggest metallic copper surfaces with moderate chlorine coverage and oxychloride-like clusters are active sites responsible for the promotional effect. These findings may facilitate structure-performance relationships, forwarding the next generation of this family of catalysts.
A global analysis of the rise, reign, and retreat of topics in research toward sustainable platform chemicals
Tautorat, Paul; Tremolada, Benedetta; Martín Fernández, Antonio José; et al. (2025)
Green Chemistry
Platform chemicals—such as olefins, ammonia, aromatics, and methanol—serve as fundamental building blocks for the chemical industry. At the same time, they account for 4% of global CO2 emissions, highlighting the need for renewable feedstocks, renewable energy, or other alternative approaches to develop more sustainable production routes toward carbon neutrality. Despite substantial research output, we lack a holistic understanding of where innovation is heading. This gap leaves research planning and policy decisions without a quantitative basis for understanding the directions of innovation. A better understanding of how they differ between platform chemicals is critical for delineating policies and strategic plans toward a net-zero future. Our study addresses this gap by providing unprecedented clarity on global research trends in platform chemicals spanning the last three decades since the establishment of the Green Chemistry principles and other subsequent sustainability approaches for chemical systems, showing the rise, reign, and retreat of topics in this area. For this purpose, we develop a novel approach by integrating topic modelling, generative AI, and expert judgment to analyse >90 000 research articles from Scopus, identifying 62 distinct research topics and tracking their temporal and geographical trends. Our results reveal different innovation patterns across the four platform chemicals. Driven by the concepts of an ammonia or methanol economy, research output has increased for these platform chemicals by a factor of 17 and 6 between 2000 and 2024, respectively. This growth has been led by new strategies like photo- and electrochemical routes, which now account for approximately 65% of ammonia-related research. For olefins and aromatics, innovation patterns show less momentum as research has rather focused on optimising available technologies. Reliance on existing alternative routes (based on renewable methanol) and olefins and aromatics’ molecular complexity could explain this lower momentum. Our quantitative findings can help define research priorities for green chemistry and derive the implications of emerging technological trends on industrial systems regarding future electricity, biomass, and feedstock demand.
Polyethylene hydrogenolysis to liquid products over bimetallic catalysts with favorable environmental footprint and economics
Nogueroles Langa, Iris; Ge, Yuzhen; Salah, Cecilia; et al. (2025)
Nature Communications
Assessing the sustainability of plastic chemical recycling requires realistic feedstocks and catalysts designed within sustainability-led frameworks (Plastic-to-X). We link catalyst design and systems analysis to study hydrogenolysis of high-density polyethylene (virgin and bottle caps; Mw = 100–200 kDa). We report Ru–Ni alloy nanoparticles (3–4 nm) supported on titania that yield up to 55% liquid C6–C45 products under optimized conditions, whereas monometallic Ru produces virtually no liquids Operando spectroscopy and simulations reveal structure sensitivity: backbone scission follows dehydrogenation and hydrogenation cycles at defective alloy sites formed in situ. Integrating these mechanistic insights with life cycle and techno-economic analyses indicates profitable processing of plastic caps over the optimal catalyst (2.5 wt% Ru, 5 wt% Ni) with substantially lower CO2 emissions even when using green H2. Furthermore, within the Plastic-to-X framework, we identify a minimum average chain length threshold of C11 for product distributions as a critical design metric to reconcile environmental and economic objectives.
An artificial leaf device built with earth-abundant materials for combined H2 production and storage as formate with efficiency > 10%
Ampelli, Claudio; Giusi, Daniele; Miceli, Matteo; et al. (2023)
Energy & Environmental Science
A major challenge for achieving energy transition and transforming the current energy model into distributed production is the development of efficient artificial leaf-type devices capable of directly converting carbon dioxide (CO2), water and sunlight into sustainable fuels and chemicals under ambient conditions. These devices should avoid using critical raw materials to be sustainable and cost-competitive. We report top-level results for the first time in converting CO2 and H2O to fuels (formate and H-2) using sunlight and electrodes based solely on earth-abundant materials. The cell provides a solar-to-fuel efficiency of >10% combined with world-record current densities to comparable devices operating at room temperature, without adding sacrificial donors or electrical bias. In addition, we present the novel concept of producing at the same time H-2 and an H-2-storage element (formate), the latter used to produce H-2 when light is absent. This solution allows continuous (24 h) hydrogen production using an artificial-leaf device. For the first time, we show the feasibility of this solution. The experimental results were obtained in an optimised, compact electrochemical flow cell, with electrodes based on Cu-S and Ni-Fe-Zn oxide (for CO2 reduction and oxygen evolution reactions, respectively) supported on gas-diffusion substrates, integrated with a low-cost Si-based photovoltaic module. The cell design allows for easy scale-up and low manufacturing and operating costs. The cell operates at a current density of about 17 mA cm(-2) and a full-cell voltage of 2.5 V (stable for at least ten hours and in on-off operations), providing formate productivity of 193 mu mol h(-1) cm(-2), paving the way towards the implementation of affordable artificial-leaf type systems in the future energy scenario.
Energy crisis in Europe enhances the sustainability of green chemicals
Nabera, Abhinandan; Istrate, Ioan-Robert; Martín Fernández, Antonio José; et al. (2023)
Green Chemistry
Ammonia and methanol are essential to modern societies, but their production has been heavily reliant on natural gas, which contributes to supply disruptions and significant CO2 emissions. While low-carbon or green production routes have been extensively researched, their adoption has been hindered by higher costs, making them unsustainable. However, a recent energy crisis in Europe has created a unique opportunity to shift towards greener production technologies. Here we show that, green ammonia, produced through wind-powered water electrolysis, had the potential to outperform its fossil counterpart for six months as of December 2021, while methanol produced through CO2 capture and wind-based water electrolysis became an economically appealing alternative. With a coordinated effort from academia, industry, and policymakers, Europe can lead the grand transition towards more sustainable practices in the chemical industry.
CO₂ Electroreduction To Syngas With Tunable Composition In An Artificial Leaf
Veenstra, Florentine L.P.; Cibaka, Thérèse; Martín Fernández, Antonio José; et al. (2024)
ChemSusChem
Artificial leaves (a-leaves) can reduce carbon dioxide into syngas using solar power and could be combined with thermo- and biocatalytic technologies to decentralize the production of valuable products. By providing variable CO : H₂ ratios on demand, a-leaves could facilitate optimal combinations and control the distribution of products in most of these hybrid systems. However, the current design procedures of a-leaves concentrate on achieving high performance for a predetermined syngas composition. This study demonstrates that incorporating the electrolyte flow as a design variable enables flexible production without compromising performance. The concept was tested on an a-leaf using a commercial cell, a Cu₂O:Inₓ cathodic catalyst, and an inexpensive amorphous silicon thin-film photovoltaic module. Syngas with CO : H₂ ratio in the range of 1.8–2.3 could be attained with only 2 % deviation from the optimal cell voltage and controllable solely by catholyte flow. These features could be beneficial for downstream technologies such as Fischer-Tropsch synthesis and anaerobic fermentation.
Environmental and economic potential of decentralised electrocatalytic ammonia synthesis powered by solar energy
D'Angelo, Sebastiano Carlo; Martín Fernández, Antonio José; Cobo Gutiérrez, Selene; et al. (2023)
Energy & Environmental Science
Intense efforts have been devoted to developing green and blue centralised Haber-Bosch processes (gHB and bHB, respectively), but the feasibility of a decentralised and more sustainable scheme has yet to be assessed. Here we reveal the conditions under which small-scale systems (NH3-leaves) based on the electrocatalytic reduction of nitrogen (eN(2)R) powered by photovoltaic energy could realise a decentralised scheme competitive in terms of environmental and economic criteria. For this purpose, we calculated energy efficiency targets worldwide, providing clear values that may guide research in the incipient eN(2)R field. Even at this germinal stage, the NH3-leaf technology would compete favourably in sunny locations for CO2-related Earth-system processes and human health relative to the business-as-usual production scenario. Moreover, a modest 8% gain in energy efficiency would already make them outperform the gHB in terms of climate change-related impacts in the sunniest locations. If no CO2 taxation is enforced, the lowest estimated ammonia production cost would be 3 times the industrial standard, with the potential to match it provided a substantial decrease of investment costs and very high selectivity toward ammonia in eN(2)R are achieved. The disclosed sustainability potential of NH3-leaf makes it a strong ally of gHB toward defossilised ammonia production.
The Environmental Feasibility of Decentralised Solar Ammonia
D'Angelo, Sebastiano Carlo; Martín Fernández, Antonio José; Guillén Gosálbez, Gonzalo; et al. (2023)
Chimia
Intense efforts have been devoted to developing green and blue centralised Haber-Bosch processes (gHB and bHB, respectively), but the feasibility of a decentralised and sustainable scheme has yet to be assessed. Here we reveal the conditions under which small-scale systems based on the electrocatalytic reduction of nitrogen (eN2R) powered by photovoltaic energy (NH3-leaf) could become a competitive technology in terms of environmental criteria. To this end, we calculated energy efficiency targets based on solar irradiation atlases to guide research in the incipient eN2R field. Even under this germinal state, the NH3-leaf technology would compete favourably in sunny locations relative to the business-as-usual production scenario. The disclosed sustainability potential of NH3-leaf makes it a strong ally of gHB toward a non-fossil ammonia production.
Long-chain hydrocarbons by CO2 electroreduction using polarized nickel catalysts
Zhou, Yansong; Martín Fernández, Antonio José; Dattila, Federico; et al. (2022)
Nature Catalysis
The electroreduction of CO2, driven by renewable electricity, can be used to sustainably generate synthetic fuels. So far, only copper-based materials have been used to catalyse the formation of multicarbon products, albeit limited to C2 or C3 molecules. Herein, we disclose that inorganic nickel oxygenate-derived electrocatalysts can generate linear and branched C3 to C6 hydrocarbons with sustained Faradaic efficiencies of up to 6.5%, contrasting with metallic nickel, which is practically inactive. Operando X-ray absorption spectroscopy, electrochemical CO stripping and density functional theory pinpoint the presence of stable, polarized Niδ+ active sites associated with Ni–O bonds, which bind CO moderately. The reduction of selected C1 molecules and density functional theory simulations suggest that the Niδ+ sites promote a mechanism reminiscent of the Fischer–Tropsch synthesis: COOH + CHx coupling followed by successive CHx insertions. Our results disclose atom polarization to be the key that prevents the CO poisoning of nickel and enables CO2 reduction to a wider pool of valuable products.
CO₂ Electroreduction to Long-Chain Hydrocarbons on Cobalt Catalysts
Preikschas, Phil; Zhang, Jie; Seemakurthi, Ranga Rohit; et al. (2024)
Advanced Energy Materials
Renewable-powered electrocatalytic CO2 conversion to long-chain hydrocarbons represents a sustainable path to produce chemicals and fuels. However, recently discovered systems still lack C-C coupling capabilities required to yield longer, more valuable carbon chains. This study reports cobalt catalysts with a focus on a Co3O4-derived material for the selective conversion of CO2 to C-1-C-7 hydrocarbons, following an Anderson-Schulz-Flory distribution. The obtained chain growth probability (alpha) of 0.54 substantially exceeds that of any other known electrocatalyst, which ranged from 0.2 to 0.4. Detailed in situ characterization and simulations indicated that Co-Co3O4 interfaces, formed in situ during CO2 electrolysis, are the active sites that promote enhanced chain growth. To prevent overreduction that causes the deactivation of these interfacial sites, the electrode is exposed to intermittent short reoxidation cycles during CO2 electrolysis. Consequently, the catalyst regained its oxidic phase and ability to form hydrocarbons. Overall, this study opens new frontiers in the one-step conversion of CO2 into multi-carbon products and suggests the exploration of metal-metal oxide interfaces as a promising strategy for further progress.

Publications 1 - 10 of 17

Antonio José Martín Fernández

Last Name

First Name

ORCID

Organisational unit

Filters

Search Results