Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity.

Improving the kinetics and selectivity of CO2/CO electroreduction to valuable multi-carbon products is a challenge for science and is a requirement for practical relevance. Here we develop a thiol-modified surface ligand strategy that promotes electrochemical CO-to-acetate. We explore a picture wherein nucleophilic interaction between the lone pairs of sulfur and the empty orbitals of reaction intermediates contributes to making the acetate pathway more energetically accessible. Density functional theory calculations and Raman spectroscopy suggest a mechanism where the nucleophilic interaction increases the sp2 hybridization of CO(ad), facilitating the rate-determining step, CO* to (CHO)*. We find that the ligands stabilize the (HOOC-CH2)* intermediate, a key intermediate in the acetate pathway. In-situ Raman spectroscopy shows shifts in C-O, Cu-C, and C-S vibrational frequencies that agree with a picture of surface ligand-intermediate interactions. A Faradaic efficiency of 70% is obtained on optimized thiol-capped Cu catalysts, with onset potentials 100 mV lower than in the case of reference Cu catalysts.

Efficient multicarbon formation in acidic CO2 reduction via tandem electrocatalysis.

The electrochemical reduction of CO2 in acidic conditions enables high single-pass carbon efficiency. However, the competing hydrogen evolution reaction reduces selectivity in the electrochemical reduction of CO2, a reaction in which the formation of CO, and its ensuing coupling, are each essential to achieving multicarbon (C2+) product formation. These two reactions rely on distinct catalyst properties that are difficult to achieve in a single catalyst. Here we report decoupling the CO2-to-C2+ reaction into two steps, CO2-to-CO and CO-to-C2+, by deploying two distinct catalyst layers operating in tandem to achieve the desired transformation. The first catalyst, atomically dispersed cobalt phthalocyanine, reduces CO2 to CO with high selectivity. This process increases local CO availability to enhance the C-C coupling step implemented on the second catalyst layer, which is a Cu nanocatalyst with a Cu-ionomer interface. The optimized tandem electrodes achieve 61% C2H4 Faradaic efficiency and 82% C2+ Faradaic efficiency at 800 mA cm-2 at 25 °C. When optimized for single-pass utilization, the system reaches a single-pass carbon efficiency of 90 ± 3%, simultaneous with 55 ± 3% C2H4 Faradaic efficiency and a total C2+ Faradaic efficiency of 76 ± 2%, at 800 mA cm-2 with a CO2 flow rate of 2 ml min-1.

Single-site decorated copper enables energy- and carbon-efficient CO2 methanation in acidic conditions.

Renewable CH4 produced from electrocatalytic CO2 reduction is viewed as a sustainable and versatile energy carrier, compatible with existing infrastructure. However, conventional alkaline and neutral CO2-to-CH4 systems suffer CO2 loss to carbonates, and recovering the lost CO2 requires input energy exceeding the heating value of the produced CH4. Here we pursue CH4-selective electrocatalysis in acidic conditions via a coordination method, stabilizing free Cu ions by bonding Cu with multidentate donor sites. We find that hexadentate donor sites in ethylenediaminetetraacetic acid enable the chelation of Cu ions, regulating Cu cluster size and forming Cu-N/O single sites that achieve high CH4 selectivity in acidic conditions. We report a CH4 Faradaic efficiency of 71% (at 100 mA cm-2) with <3% loss in total input CO2 that results in an overall energy intensity (254 GJ/tonne CH4), half that of existing electroproduction routes.

Surface hydroxide promotes CO2 electrolysis to ethylene in acidic conditions.

Performing CO2 reduction in acidic conditions enables high single-pass CO2 conversion efficiency. However, a faster kinetics of the hydrogen evolution reaction compared to CO2 reduction limits the selectivity toward multicarbon products. Prior studies have shown that adsorbed hydroxide on the Cu surface promotes CO2 reduction in neutral and alkaline conditions. We posited that limited adsorbed hydroxide species in acidic CO2 reduction could contribute to a low selectivity to multicarbon products. Here we report an electrodeposited Cu catalyst that suppresses hydrogen formation and promotes selective CO2 reduction in acidic conditions. Using in situ time-resolved Raman spectroscopy, we show that a high concentration of CO and OH on the catalyst surface promotes C-C coupling, a finding that we correlate with evidence of increased CO residence time. The optimized electrodeposited Cu catalyst achieves a 60% faradaic efficiency for ethylene and 90% for multicarbon products. When deployed in a slim flow cell, the catalyst attains a 20% energy efficiency to ethylene, and 30% to multicarbon products.

Doping Shortens the Metal/Metal Distance and Promotes OH Coverage in Non-Noble Acidic Oxygen Evolution Reaction Catalysts.

Acidic water electrolysis enables the production of hydrogen for use as a chemical and as a fuel. The acidic environment hinders water electrolysis on non-noble catalysts, a result of the sluggish kinetics associated with the adsorbate evolution mechanism, reliant as it is on four concerted proton-electron transfer steps. Enabling a faster mechanism with non-noble catalysts will help to further advance acidic water electrolysis. Here, we report evidence that doping Ba cations into a Co3O4 framework to form Co3-xBaxO4 promotes the oxide path mechanism and simultaneously improves activity in acidic electrolytes. Co3-xBaxO4 catalysts reported herein exhibit an overpotential of 278 mV at 10 mA/cm2 in 0.5 M H2SO4 electrolyte and are stable over 110 h of continuous water oxidation operation. We find that the incorporation of Ba cations shortens the Co-Co distance and promotes OH adsorption, findings we link to improved water oxidation in acidic electrolyte.

High-Density Cobalt Single-Atom Catalysts for Enhanced Oxygen Evolution Reaction.

Single atom catalysts (SACs) possess unique catalytic properties due to low-coordination and unsaturated active sites. However, the demonstrated performance of SACs is limited by low SAC loading, poor metal-support interactions, and nonstable performance. Herein, we report a macromolecule-assisted SAC synthesis approach that enabled us to demonstrate high-density Co single atoms (10.6 wt % Co SAC) in a pyridinic N-rich graphenic network. The highly porous carbon network (surface area of ∼186 m2 g-1) with increased conjugation and vicinal Co site decoration in Co SACs significantly enhanced the electrocatalytic oxygen evolution reaction (OER) in 1 M KOH (η10 at 351 mV; mass activity of 2209 mA mgCo-1 at 1.65 V) with more than 300 h stability. Operando X-ray absorption near-edge structure demonstrates the formation of electron-deficient Co-O coordination intermediates, accelerating OER kinetics. Density functional theory (DFT) calculations reveal the facile electron transfer from cobalt to oxygen species-accelerated OER.

Epitaxially grown silicon-based single-atom catalyst for visible-light-driven syngas production.

Improving the dispersion of active sites simultaneous with the efficient harvest of photons is a key priority for photocatalysis. Crystalline silicon is abundant on Earth and has a suitable bandgap. However, silicon-based photocatalysts combined with metal elements has proved challenging due to silicon's rigid crystal structure and high formation energy. Here we report a solid-state chemistry that produces crystalline silicon with well-dispersed Co atoms. Isolated Co sites in silicon are obtained through the in-situ formation of CoSi2 intermediate nanodomains that function as seeds, leading to the production of Co-incorporating silicon nanocrystals at the CoSi2/Si epitaxial interface. As a result, cobalt-on-silicon single-atom catalysts achieve an external quantum efficiency of 10% for CO2-to-syngas conversion, with CO and H2 yields of 4.7 mol g(Co)-1 and 4.4 mol g(Co)-1, respectively. Moreover, the H2/CO ratio is tunable between 0.8 and 2. This photocatalyst also achieves a corresponding turnover number of 2 × 104 for visible-light-driven CO2 reduction over 6 h, which is over ten times higher than previously reported single-atom photocatalysts.

Strong-Proton-Adsorption Co-Based Electrocatalysts Achieve Active and Stable Neutral Seawater Splitting.

Direct electrolysis of pH-neutral seawater to generate hydrogen is an attractive approach for storing renewable energy. However, due to the anodic competition between the chlorine evolution and the oxygen evolution reaction (OER), direct seawater splitting suffers from a low current density and limited operating stability. Exploration of catalysts enabling an OER overpotential below the hypochlorite formation overpotential (≈490 mV) is critical to suppress the chloride evolution and facilitate seawater splitting. Here, a proton-adsorption-promoting strategy to increase the OER rate is reported, resulting in a promoted and more stable neutral seawater splitting. The best catalysts herein are strong-proton-adsorption (SPA) materials such as palladium-doped cobalt oxide (Co3- x Pdx O4 ) catalysts. These achieve an OER overpotential of 370 mV at 10 mA cm-2 in pH-neutral simulated seawater, outperforming Co3 O4 by a margin of 70 mV. Co3- x Pdx O4 catalysts provide stable catalytic performance for 450 h at 200 mA cm-2 and 20 h at 1 A cm-2 in neutral seawater. Experimental studies and theoretical calculations suggest that the incorporation of SPA cations accelerates the rate-determining water dissociation step in neutral OER pathway, and control studies rule out the provision of additional OER sites as a main factor herein.

Germanium silicon oxide achieves multi-coloured ultra-long phosphorescence and delayed fluorescence at high temperature.

Colour-tuned phosphors are promising for advanced security applications such as multi-modal anti-counterfeiting and data encryption. The practical adoption of colour-tuned phosphors requires these materials to be responsive to multiple stimuli (e.g., excitation wavelength, excitation waveform, and temperature) and exhibit excellent materials stability simultaneously. Here we report germanium silicon oxide (GSO) - a heavy-metal-free inorganic phosphor - that exhibits colour-tuned ultra-long phosphorescence and delayed fluorescence across a broad temperature range (300 - 500 K) in air. We developed a sol-gel processing strategy to prepare amorphous oxides containing homogeneously dispersed Si and Ge atoms. The co-existence of Ge and Si luminescent centres (LC) leads to an excitation-dependent luminescence change across the UV-to-visible region. GSO exhibits Si LC-related ultra-long phosphorescence at room-temperature and thermally activated delayed fluorescence at temperatures as high as 573 K. This long-lived PL is sensitized via the energy transfer from Ge defects to Si LCs, which provides PL lifetime tunability for GSO phosphors. The oxide scaffold of GSO offers 500-day materials stability in air; and 1-week stability in strong acidic and basic solutions. Using GSO/polymer hybrids, we demonstrated colour-tuned security tags whose emission wavelength and lifetime can be controlled via the excitation wavelength, and temperature, indicating promise in security applications.

Fast Near-Infrared Photodetection Using III-V Colloidal Quantum Dots.

Colloidal quantum dots (CQDs) are promising materials for infrared (IR) light detection due to their tunable bandgap and their solution processing; however, to date, the time response of CQD IR photodiodes is inferior to that provided by Si and InGaAs. It is reasoned that the high permittivity of II-VI CQDs leads to slow charge extraction due to screening and capacitance, whereas III-Vs-if their surface chemistry can be mastered-offer a low permittivity and thus increase potential for high-speed operation. In initial studies, it is found that the covalent character in indium arsenide (InAs) leads to imbalanced charge transport, the result of unpassivated surfaces, and uncontrolled heavy doping. Surface management using amphoteric ligand coordination is reported, and it is found that the approach addresses simultaneously the In and As surface dangling bonds. The new InAs CQD solids combine high mobility (0.04 cm2 V-1 s-1 ) with a 4× reduction in permittivity compared to PbS CQDs. The resulting photodiodes achieve a response time faster than 2 ns-the fastest photodiode among previously reported CQD photodiodes-combined with an external quantum efficiency (EQE) of 30% at 940 nm.

Stabilizing Hydrous ß-NiOOH for Efficient Electrocatalytic Water Oxidation by Integrating Y and Co into Amorphous Ni-Based Nanoparticles.

A two-stage ball milling process was used to synthesize amorphous Ni79.2Nb12.5Y8.3 and Ni74.2Co5Nb12.5Y8.3 nanoparticles from elemental powders. The two-stage ball milling process provides a scalable and industrially applicable method for producing non-metalloid amorphous nanoparticles. The amorphous nanoparticles displayed excellent catalytic performance toward the oxygen evolution reaction (OER) in 1 M KOH, displaying lower overpotentials than IrO2 at 10 mA cm-2. The addition of Co in the amorphous alloy reduced the overpotential to 288 mV at 10 mA cm-2. The pairing of X-ray photoelectron spectroscopy and in situ X-ray absorption spectroscopy revealed that the improved OER activity of amorphous Ni74.2Co5Nb12.5Y8.3 was attributed to the catalytic synergy between Y and Co. The integration of Y supported proton-coupled electron-transfer processes that assisted with the electrostatic adsorption of OH- and formation of oxyhydroxide species, while Co sites enabled metal-oxo bonding to prevent Ni overcharging and the stabilization of ß-NiOOH. The catalytic synergy between Y and Co reduces the amount of Co needed to enhance the OER activity of Ni-based alloys and lessens the dependence on Co, which is in high demand in many renewable energy and storage applications.

Early Transition-Metal-Based Binary Oxide/Nitride for Efficient Electrocatalytic Hydrogen Evolution from Saline Water in Different pH Environments.

Using abundant seawater can reduce reliance on freshwater resources for hydrogen production from electrocatalytic water splitting. However, seawater has detrimental effects on the stability and activity of the hydrogen evolution reaction (HER) electrocatalysts under different pH conditions. In this work, we report the synthesis of binary metallic core-sheath nitride@oxynitride electrocatalysts [Ni(ETM)]δ+-[O-N]δ-, where ETM is an early transition metal V or Cr. Using NiVN on a nickel foam (NF) substrate, we demonstrate an HER overpotential as low as 32 mV at -10 mA cm-2 in saline water (0.6 M NaCl). The results represent an advancement in saline water HER performance of earth-abundant electrocatalysts, especially under near-neutral pH range (i.e., pH 6-8). Doping ETMs in nickel oxynitrides accelerates the typically rate-determining H2O dissociation step for HER and suppresses chloride deactivation of the catalyst in neutral-pH saline water. Heterointerface synergism occurs through H2O adsorption and dissociation at interfacial oxide character, while adsorbed H* proceeds via Heyrovsky or Tafel step on the nitride character. This electrocatalyst showed stable performance under a constant current density of -50 mA cm-2 for 50 h followed by additional 50 h at -100 mA cm-2 in a neutral saline electrolyte (1 M PB + 0.6 M NaCl). Contrarily, under the same conditions, Pt/C@NF exhibited significantly low performance after a mere 4 h at -50 mA cm-2. The low Tafel slope of 25 mV dec-1 indicated that the reaction is Tafel limited, unlike commercial Pt/C, which is Heyrovsky limited. We close by discussing general principles concerning surface charge delocalization for the design of HER electrocatalysts in pH saline environments.

Ternary Alloys Enable Efficient Production of Methoxylated Chemicals via Selective Electrocatalytic Hydrogenation of Lignin Monomers.

We explore the selective electrocatalytic hydrogenation of lignin monomers to methoxylated chemicals, of particular interest, when powered by renewable electricity. Prior studies, while advancing the field rapidly, have so far lacked the needed selectivity: when hydrogenating lignin-derived methoxylated monomers to methoxylated cyclohexanes, the desired methoxy group (-OCH3) has also been reduced. The ternary PtRhAu electrocatalysts developed herein selectively hydrogenate lignin monomers to methoxylated cyclohexanes-molecules with uses in pharmaceutics. Using X-ray absorption spectroscopy and in situ Raman spectroscopy, we find that Rh and Au modulate the electronic structure of Pt and that this modulating steers intermediate energetics on the electrocatalyst surface to facilitate the hydrogenation of lignin monomers and suppress C-OCH3 bond cleavage. As a result, PtRhAu electrocatalysts achieve a record 58% faradaic efficiency (FE) toward 2-methoxycyclohexanol from the lignin monomer guaiacol at 200 mA cm-2, representing a 1.9× advance in FE and a 4× increase in partial current density compared to the highest productivity prior reports. We demonstrate an integrated lignin biorefinery where wood-derived lignin monomers are selectively hydrogenated and funneled to methoxylated 2-methoxy-4-propylcyclohexanol using PtRhAu electrocatalysts. This work offers an opportunity for the sustainable electrocatalytic synthesis of methoxylated pharmaceuticals from renewable biomass.

Boride-derived oxygen-evolution catalysts.

Metal borides/borates have been considered promising as oxygen evolution reaction catalysts; however, to date, there is a dearth of evidence of long-term stability at practical current densities. Here we report a phase composition modulation approach to fabricate effective borides/borates-based catalysts. We find that metal borides in-situ formed metal borates are responsible for their high activity. This knowledge prompts us to synthesize NiFe-Boride, and to use it as a templating precursor to form an active NiFe-Borate catalyst. This boride-derived oxide catalyzes oxygen evolution with an overpotential of 167 mV at 10 mA/cm2 in 1 M KOH electrolyte and requires a record-low overpotential of 460 mV to maintain water splitting performance for over 400 h at current density of 1 A/cm2. We couple the catalyst with CO reduction in an alkaline membrane electrode assembly electrolyser, reporting stable C2H4 electrosynthesis at current density 200 mA/cm2 for over 80 h.

In Situ Formation of Nano Ni-Co Oxyhydroxide Enables Water Oxidation Electrocatalysts Durable at High Current Densities.

The oxygen evolution reaction (OER) limits the energy efficiency of electrocatalytic systems due to the high overpotential symptomatic of poor reaction kinetics; this problem worsens over time if the performance of the OER electrocatalyst diminishes during operation. Here, a novel synthesis of nanocrystalline Ni-Co-Se using ball milling at cryogenic temperature is reported. It is discovered that, by anodizing the Ni-Co-Se structure during OER, Se ions leach out of the original structure, allowing water molecules to hydrate Ni and Co defective sites, and the nanoparticles to evolve into an active Ni-Co oxyhydroxide. This transformation is observed using operando X-ray absorption spectroscopy, with the findings confirmed using density functional theory calculations. The resulting electrocatalyst exhibits an overpotential of 279 mV at 0.5 A cm-2 and 329 mV at 1 A cm-2 and sustained performance for 500 h. This is achieved using low mass loadings (0.36 mg cm-2 ) of cobalt. Incorporating the electrocatalyst in an anion exchange membrane water electrolyzer yields a current density of 1 A cm-2 at 1.75 V for 95 h without decay in performance. When the electrocatalyst is integrated into a CO2 -to-ethylene electrolyzer, a record-setting full cell voltage of 3 V at current density 1 A cm-2 is achieved.

Quantum Dot Self-Assembly Enables Low-Threshold Lasing.

Perovskite quantum dots (QDs) are of interest for solution-processed lasers; however, their short Auger lifetime has limited lasing operation principally to the femtosecond temporal regime the photoexcitation levels to achieve optical gain threshold are up to two orders of magnitude higher in the nanosecond regime than in the femtosecond. Here the authors report QD superlattices in which the gain medium facilitates excitonic delocalization to decrease Auger recombination and in which the macroscopic dimensions of the structures provide the optical feedback required for lasing. The authors develope a self-assembly strategy that relies on sodiumd-an assembly director that passivates the surface of the QDs and induces self-assembly to form ordered three-dimensional cubic structures. A density functional theory model that accounts for the attraction forces between QDs allows to explain self-assembly and superlattice formation. Compared to conventional organic-ligand-passivated QDs, sodium enables higher attractive forces, ultimately leading to the formation of micron-length scale structures and the optical faceting required for feedback. Simultaneously, the decreased inter-dot distance enabled by the new ligand enhances exciton delocalization among QDs, as demonstrated by the dynamically red-shifted photoluminescence. These structures function as the lasing cavity and the gain medium, enabling nanosecond-sustained lasing with a threshold of 25 µJ cm-2 .

Low coordination number copper catalysts for electrochemical CO2 methanation in a membrane electrode assembly.

The electrochemical conversion of CO2 to methane provides a means to store intermittent renewable electricity in the form of a carbon-neutral hydrocarbon fuel that benefits from an established global distribution network. The stability and selectivity of reported approaches reside below technoeconomic-related requirements. Membrane electrode assembly-based reactors offer a known path to stability; however, highly alkaline conditions on the cathode favour C-C coupling and multi-carbon products. In computational studies herein, we find that copper in a low coordination number favours methane even under highly alkaline conditions. Experimentally, we develop a carbon nanoparticle moderator strategy that confines a copper-complex catalyst when employed in a membrane electrode assembly. In-situ XAS measurements confirm that increased carbon nanoparticle loadings can reduce the metallic copper coordination number. At a copper coordination number of 4.2 we demonstrate a CO2-to-methane selectivity of 62%, a methane partial current density of 136 mA cm-2, and > 110 hours of stable operation.

Stabilizing Highly Active Ru Sites by Suppressing Lattice Oxygen Participation in Acidic Water Oxidation.

In hydrogen production, the anodic oxygen evolution reaction (OER) limits the energy conversion efficiency and also impacts stability in proton-exchange membrane water electrolyzers. Widely used Ir-based catalysts suffer from insufficient activity, while more active Ru-based catalysts tend to dissolve under OER conditions. This has been associated with the participation of lattice oxygen (lattice oxygen oxidation mechanism (LOM)), which may lead to the collapse of the crystal structure and accelerate the leaching of active Ru species, leading to low operating stability. Here we develop Sr-Ru-Ir ternary oxide electrocatalysts that achieve high OER activity and stability in acidic electrolyte. The catalysts achieve an overpotential of 190 mV at 10 mA cm-2 and the overpotential remains below 225 mV following 1,500 h of operation. X-ray absorption spectroscopy and 18O isotope-labeled online mass spectroscopy studies reveal that the participation of lattice oxygen during OER was suppressed by interactions in the Ru-O-Ir local structure, offering a picture of how stability was improved. The electronic structure of active Ru sites was modulated by Sr and Ir, optimizing the binding energetics of OER oxo-intermediates.

Promoting CO2 methanation via ligand-stabilized metal oxide clusters as hydrogen-donating motifs.

Electroreduction uses renewable energy to upgrade carbon dioxide to value-added chemicals and fuels. Renewable methane synthesized using such a route stands to be readily deployed using existing infrastructure for the distribution and utilization of natural gas. Here we design a suite of ligand-stabilized metal oxide clusters and find that these modulate carbon dioxide reduction pathways on a copper catalyst, enabling thereby a record activity for methane electroproduction. Density functional theory calculations show adsorbed hydrogen donation from clusters to copper active sites for the *CO hydrogenation pathway towards *CHO. We promote this effect via control over cluster size and composition and demonstrate the effect on metal oxides including cobalt(II), molybdenum(VI), tungsten(VI), nickel(II) and palladium(II) oxides. We report a carbon dioxide-to-methane faradaic efficiency of 60% at a partial current density to methane of 135 milliampere per square centimetre. We showcase operation over 18 h that retains a faradaic efficiency exceeding 55%.

Recent Advances in the Design of Plasmonic Au/TiO2 Nanostructures for Enhanced Photocatalytic Water Splitting.

Plasmonic nanostructures have played a key role in extending the activity of photocatalysts to the visible light spectrum, preventing the electron-hole combination and providing with hot electrons to the photocatalysts, a crucial step towards efficient broadband photocatalysis. One plasmonic photocatalyst, Au/TiO2, is of a particular interest because it combines chemical stability, suitable electronic structure, and photoactivity for a wide range of catalytic reactions such as water splitting. In this review, we describe key mechanisms involving plasmonics to enhance photocatalytic properties leading to efficient water splitting such as production and transport of hot electrons through advanced analytical techniques used to probe the photoactivity of plasmonics in engineered Au/TiO2 devices. This work also discusses the emerging strategies to better design plasmonic photocatalysts and understand the underlying mechanisms behind the enhanced photoactivity of plasmon-assisted catalysts.