Roberto Schimmenti

Bio: Roberto Schimmenti is an academic researcher from University of Wisconsin-Madison. The author has contributed to research in topics: Catalysis & Formate. The author has an hindex of 8, co-authored 17 publications receiving 257 citations. Previous affiliations of Roberto Schimmenti include University of Palermo & University of Catania.

Bismuthene for highly efficient carbon dioxide electroreduction reaction

Abstract: Bismuth (Bi) has been known as a highly efficient electrocatalyst for CO2 reduction reaction. Stable free-standing two-dimensional Bi monolayer (Bismuthene) structures have been predicted theoretically, but never realized experimentally. Here, we show the first simple large-scale synthesis of free-standing Bismuthene, to our knowledge, and demonstrate its high electrocatalytic efficiency for formate (HCOO−) formation from CO2 reduction reaction. The catalytic performance is evident by the high Faradaic efficiency (99% at −580 mV vs. Reversible Hydrogen Electrode (RHE)), small onset overpotential (<90 mV) and high durability (no performance decay after 75 h and annealing at 400 °C). Density functional theory calculations show the structure-sensitivity of the CO2 reduction reaction over Bismuthene and thicker nanosheets, suggesting that selective formation of HCOO− indeed can proceed easily on Bismuthene (111) facet due to the unique compressive strain. This work paves the way for the extensive experimental investigation of Bismuthene in many different fields. Stable free-standing two-dimensional Bi monolayer (Bismuthene) structures have been predicted theoretically, but never realized experimentally. Here, the authors show a large-scale synthesis of free-standing Bismuthene and its electrocatalytic activity for CO2 reduction to formate.

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies.

Abstract: Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

Eliminating dissolution of platinum-based electrocatalysts at the atomic scale

Abstract: A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. This mitigation strategy was applied towards 3 nm Pt3Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V. Deployment of proton-exchange membrane fuel cells is limited by the durability of Pt-nanoscale catalysts during cathodic oxygen reduction reactions. Dissolution processes on single crystalline and thin film surfaces are now correlated leading to the design of PtAu catalysts with suppressed dissolution.

A completely precious metal–free alkaline fuel cell with enhanced performance using a carbon-coated nickel anode

Abstract: Significance We present a groundbreaking advance in completely nonprecious hydrogen fuel cell technologies achieving a record power density of 200 mW/cm2 with Ni@CNx anode and Co−Mn cathode. The 2-nm CNx coating weakens the O-binding energy, which effectively mitigates the undesirable surface oxidation during hydrogen oxidation reaction (HOR) polarization, leading to a stable fuel cell operation for Ni@CNx over 100 h at 200 mA/cm2, superior to a Ni nanoparticle counterpart. Ni@CNx exhibited a dramatically enhanced tolerance to CO relative to Pt/C, enabling the use of hydrogen gas with trace amounts of CO, critical for practical applications. The complete removal of precious metals in fuel cells lowers the catalyst cost to virtually negligible levels and marks a milestone for practical alkaline fuel cells.

Solution-Phase Synthesis of PdH0.706 Nanocubes with Enhanced Stability and Activity toward Formic Acid Oxidation.

Abstract: Palladium is one of the few metals capable of forming hydrides, with the catalytic properties being dependent on the elemental composition and spatial distribution of H atoms in the lattice. Herein, we report a facile method for the complete transformation of Pd nanocubes into a stable phase made of PdH0.706 by treating them with aqueous hydrazine at a concentration as low as 9.2 mM. Using formic acid oxidation (FAO) as a model reaction, we systematically investigated the structure-catalytic property relationship of the resultant nanocubes with different degrees of hydride formation. The current density at 0.4 V was enhanced by four times when the nanocubes were completely converted from Pd to PdH0.706. On the basis of a set of slab models with PdH(100) overlayers on Pd(100), we conducted density functional theory calculations to demonstrate that the degree of hybrid formation could influence both the activity and selectivity toward FAO by modulating the relative stability of formate (HCOO) and carboxyl (COOH) intermediates. This work provides a viable strategy for augmenting the performance of Pd-based catalysts toward various reactions without altering the loading of this scarce metal.

Industrial carbon dioxide capture and utilization: state of the art and future challenges

Abstract: Dramatically increased CO2 concentration from several point sources is perceived to cause severe greenhouse effect towards the serious ongoing global warming with associated climate destabilization, inducing undesirable natural calamities, melting of glaciers, and extreme weather patterns. CO2 capture and utilization (CCU) has received tremendous attention due to its significant role in intensifying global warming. Considering the lack of a timely review on the state-of-the-art progress of promising CCU techniques, developing an appropriate and prompt summary of such advanced techniques with a comprehensive understanding is necessary. Thus, it is imperative to provide a timely review, given the fast growth of sophisticated CO2 capture and utilization materials and their implementation. In this work, we critically summarized and comprehensively reviewed the characteristics and performance of both liquid and solid CO2 adsorbents with possible schemes for the improvement of their CO2 capture ability and advances in CO2 utilization. Their industrial applications in pre- and post-combustion CO2 capture as well as utilization were systematically discussed and compared. With our great effort, this review would be of significant importance for academic researchers for obtaining an overall understanding of the current developments and future trends of CCU. This work is bound to benefit researchers in fields relating to CCU and facilitate the progress of significant breakthroughs in both fundamental research and commercial applications to deliver perspective views for future scientific and industrial advances in CCU.

Electrocatalysis for CO2 conversion: from fundamentals to value-added products

Abstract: The continuously increasing CO2 released from human activities poses a great threat to human survival by fluctuating global climate and disturbing carbon balance among the four reservoirs of the biosphere, earth, air, and water. Converting CO2 to value-added feedstocks via electrocatalysis of the CO2 reduction reaction (CO2RR) has been regarded as one of the most attractive routes to re-balance the carbon cycle, thanks to its multiple advantages of mild operating conditions, easy handling, tunable products and the potential of synergy with the rapidly increasing renewable energy (i.e., solar, wind). Instead of focusing on a special topic of electrocatalysts for the CO2RR that have been extensively reviewed elsewhere, we herein present a rather comprehensive review of the recent research progress, in the view of associated value-added products upon selective electrocatalytic CO2 conversion. We initially provide an overview of the history and the fundamental science regarding the electrocatalytic CO2RR, with a special introduction to the design, preparation, and performance evaluation of electrocatalysts, the factors influencing the CO2RR, and the associated theoretical calculations. Emphasis will then be given to the emerging trends of selective electrocatalytic conversion of CO2 into a variety of value-added products. The structure-performance relationship and mechanism will also be discussed and investigated. The outlooks for CO2 electrocatalysis, including the challenges and opportunities in the development of new electrocatalysts, electrolyzers, the recently rising operando fundamental studies, and the feasibility of industrial applications are finally summarized.

The polyol process: a unique method for easy access to metal nanoparticles with tailored sizes, shapes and compositions.

Abstract: After about three decades of development, the polyol process is now widely recognized and practised as a unique soft chemical method for the preparation of a large variety of nanoparticles which can be used in important technological fields. It offers many advantages: low cost, ease of use and, very importantly, already proven scalability for industrial applications. Among the different classes of inorganic nanoparticles which can be prepared in liquid polyols, metals were the first reported. This review aims to give a comprehensive account of the strategies used to prepare monometallic nanoparticles and multimetallic materials with tailored size and shape. As regards monometallic materials, while the preparation of noble as well as ferromagnetic metals is now clearly established, the scope of the polyol process has been extended to the preparation of more electropositive metals, such as post-transition metals and semi-metals. The potential of this method is also clearly displayed for the preparation of alloys, intermetallics and core–shell nanostructures with a very large diversity of compositions and architectures.

Challenges in applying highly active Pt-based nanostructured catalysts for oxygen reduction reactions to fuel cell vehicles.

Abstract: The past 30 years have seen progress in the development of Pt-based nanocatalysts for the oxygen reduction reaction, and some are now in production on a commercial basis and used for polymer electrolyte fuel cells (PEFCs) for automotives and other applications. Further improvements in catalytic activity are required for wider uptake of PEFCs, however. In laboratories, researchers have developed various catalysts that have much higher activities than commercial ones, and these state-of-the-art catalysts have potential to improve energy conversion efficiencies and reduce the usage of platinum in PEFCs. There are several technical issues that must be solved before they can be applied in fuel cell vehicles, which require a high power density and practical durability, as well as high efficiency. In this Review, the development history of Pt-based nanocatalysts and recent analytical studies are summarized to identify the origin of these technical issues. Promising strategies for overcoming those issues are also discussed. This Review summarizes the development history of Pt-based nanocatalysts and recent analytical studies to identify the technical issues in the automobile application, proposing promising strategies for overcoming the trade-offs among the efficiency,power density, and durability of polymer electrolyte fuel cells.