Nathanael C. Ramos

High-entropy oxides (HEOs) offer vast compositional design space for discovering emergent functionalities, yet their controlled nanoscale synthesis remains challenging. Here, we develop a generalizable colloidal strategy that enables precision synthesis of HEO nanocrystals with compositions spanning quinary to septenary systems. Mechanistic studies reveal that differences in precursor reactivity drive a multistage growth pathway and that cooperative multimetal chemistry─where one metal initiates single-phase nucleation and a vacancy-forming metal promotes cation redistribution during growth─enables homogeneous multication incorporation. The resulting rocksalt HEO nanocrystals can be transformed into spinel phases and exhibit excellent oxygen-evolution reaction activity. Machine-learning-accelerated theoretical analysis and operando characterization identify Co–Co bridge sites on spinel {111} facets as the dominant oxygen-evolution active motifs operating through a lattice oxygen-mediated mechanism. These findings establish guiding principles for controlling nucleation, cation mixing, and active-site formation in compositionally complex oxides, enabling the rational design and data-driven optimization of high-entropy materials.

Electrocatalytic reactions involve interfacial interactions between the surfaces of electrodes and reactive species at an electrolyte interface. There are presently no universal or unambiguous methods to directly assay the active top atomic layer composition that influences the reactivity of these electrodes under relevant operating conditions. Low-energy ion scattering (LEIS) spectroscopy is a surface characterization technique that yields compositional analysis of the outermost atomic layer of a material, but it must be performed in ultrahigh vacuum (UHV). Application of LEIS measurements to electrochemical materials that are removed from ambient liquid-phase environments thus leaves an open question as to whether the surface that is transferred to UHV is truly the surface that manifested during the electrochemical reaction. Toward the goal of preserving the active surface state, we developed a sample transfer workflow for LEIS enabling air-free removal and drying of an electrode from an electrochemical cell while maintaining control of the potential using an auxiliary electrode. The potential-controlled emersion method was demonstrated to give distinct potential-dependent surface compositions for a Cu–Pd alloy relative to removal after uncontrolled return to open-circuit potential. A Cu-enriched surface was found at anodic potential and a Pd-enriched surface at cathodic potential, suggesting that the approach can be used to retain representative atomic configurations during transfer. Since adsorbates will often persist from the reaction environment, conventional sample pretreatment methods for removal, including atomic O and atomic H exposure, were also contrasted. Both methods were found to differ with results from incidental low-dose depth profiling by the LEIS primary ion source, which removes adventitious species and surface atoms during the course of repeated measurements. These depth profiles were found to be sensitive to sample history and thus qualitatively informative, despite the possible changes induced by ion damage. The results exhibit (i) the need for complete control over the polarization state of the sample at all times (no excursions to open circuit during transfer) and (ii) the utility of low-dose depth profiling to capture changes in the near-surface composition.

Aldehydes are selectively oxidized to carboxylates on group 11 metals at low potentials (2 gas from the aldehyde, known as electro-oxidative dehydrogenation (EOD) or anodic hydrogen production. The EOD process occurs with transfer of only one electron per aldehyde, whereas typical oxidation with discharge of hydrogen to form water is a two-electron process. Here, we study the catalytic activity and selectivity toward H₂ of Au, Ag, and Cu electrodes using benzaldehyde with rotating disk and ring-disk electrode (RDE/RRDE) techniques. The average number of electrons per benzaldehyde molecule obtained via H₂ detection by RRDE agrees with that obtained via Koutecký-Levich analysis conducted at various rotation rates. We find that Au and Ag have much higher H₂ and benzoate formation rates than Cu, but that Cu can perform the reaction at about 0.2 V lower overpotentials. On all three materials, benzaldehyde oxidation has high selectivity to anodic H₂ (one-electron pathway) below ∼0.5 V vs. RHE, but, with increasing potential, the selectivity shifts to H-oxidation forming water (two-electron pathway).

ConspectusDespite the growing deployment of renewable energy conversion technologies, a number of large industrial sectors remain challenging to decarbonize. Aviation, heavy transport, and the production of steel, cement, and chemicals are heavily dependent on carbon-containing fuels and feedstocks. A hopeful avenue toward carbon neutrality is the implementation of renewable carbon for the synthesis of critical fuels, chemicals, and materials. Biomass provides an opportune source of renewable carbon, naturally capturing atmospheric CO₂ and forming multicarbon linkages and useful chemical functional groups. The constituent molecules nonetheless require various chemical transformations, often best facilitated by catalytic nanomaterials, in order to access usable final products.Catalyzed transformations of renewable biomass compounds may intersect with renewable energy production by offering a means to utilize excess intermittent electricity and store it within chemical bonds. Electrochemical catalytic processes can often offer advantages in energy efficiency, product selectivity, and modular scalability compared to thermal-driven reactions. Electrocatalytic reactions with renewable carbon feedstocks can further enable related processes such as water splitting, where value-adding organic oxidation reactions may replace the evolution of oxygen. Organic electroreduction reactions may also allow desirable hydrogenations of bonds without intermediate formation of H₂ and need for additional reactors.This Account highlights recent work aimed at gaining a fundamental understanding of transformations involving biomass-derived molecules in electrocatalytic nanomaterials. Particular emphasis is placed on the oxidation of biomass derived furanic compounds such as furfural and 5-hydroxymethylfurfural (HMF), which can yield value-added chemicals, including furoic acid (FA), maleic acid (MA), and 2,5-furandicarboxylic acid (FDCA) for renewable materials and other commodities. We highlight advanced implementations of online electrochemical mass spectrometry (OLEMS) and vibrational spectroscopies such as attenuated total reflectance surface enhanced infrared reflection absorption spectroscopy (ATR-SEIRAS), combined with microkinetic models (MKMs) and quantum chemical calculations, to shed light on the elementary mechanistic pathways involved in electrochemical biomass conversion and how these paths are influenced by catalytic nanomaterials. Perspectives are given on the potential opportunities for materials development toward more efficient and selective carbon-mitigating reaction pathways.

Self-assembled monolayers (SAMs) of thiolates have increasingly been used for modification of metal surfaces in electrochemical applications including selective catalysis (e.g., CO₂ reduction, nitrogen reduction) and chemical sensing. Here, the stable electrochemical potential window of thiolate SAMs on Au, Pt, and Cu electrodes is systematically studied for a variety of thiols in aqueous electrolyte systems. For fixed tail-group functionality, the reductive stability of thiolate SAMs is found to follow the trend Au < Pt < Cu; this can be understood by considering the combined influences of the binding strength of sulfur and competitive adsorption of hydrogen. The oxidative stability of thiolate SAMs is found to follow the order: Cu < Pt < Au, consistent with each surface's propensity toward surface oxide formation. The stable reductive and oxidative potential limits are both found to vary linearly with pH, except for reduction above pH ∼10, which is independent of pH for most thiol compositions. The electrochemical stability across different functionalized thiols is then revealed to depend on many different factors including SAM defects (accessible surface metal atom sites decrease stability), intermolecular interactions (hydrophilic groups reduce the stability), and SAM thickness (stability increases with alkanethiol carbon chain length) as well as factors such as SAM-induced surface reconstruction and the ability to directly oxidize or reduce the non-sulfur part of the SAM molecule.