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.

Efficient Methane Electrosynthesis Enabled by Tuning Local CO2 Availability.

The electroreduction of carbon dioxide (CO2RR) to valuable chemicals is a promising avenue for the storage of intermittent renewable electricity. Renewable methane, obtained via CO2RR using renewable electricity as energy input, has the potential to serve as a carbon-neutral fuel or chemical feedstock, and it is of particular interest in view of the well-established infrastructure for its storage, distribution, and utilization. However, CO2RR to methane still suffers from low selectivity at commercially relevant current densities (>100 mA cm-2). Density functional theory calculations herein reveal that lowering *CO2 coverage on the Cu surface decreases the coverage of the *CO intermediate, and then this favors the protonation of *CO to *CHO, a key intermediate for methane generation, compared to the competing step, C-C coupling. We therefore pursue an experimental strategy wherein we control local CO2 availability on a Cu catalyst by tuning the concentration of CO2 in the gas stream and regulate the reaction rate through the current density. We achieve as a result a methane Faradaic efficiency (FE) of (48 ± 2)% with a partial current density of (108 ± 5) mA cm-2 and a methane cathodic energy efficiency of 20% using a dilute CO2 gas stream. We report stable methane electrosynthesis for 22 h. These findings offer routes to produce methane with high FE and high conversion rate in CO2RR and also make direct use of dilute CO2 feedstocks.

Origins of Stokes Shift in PbS Nanocrystals.

Stokes shift, an energy difference between the excitonic absorption and emission, is a property of colloidal quantum dots (CQDs) typically ascribed to splitting between dark and bright excitons. In some materials, e.g., PbS, CuInS2, and CdHgTe, a Stokes shift of up to 200 meV is observed, substantially larger than the estimates of dark-bright state splitting or vibronic relaxations. The shift origin remains highly debated because contradictory signatures of both surface and bulk character were reported for the Stokes-shifted electronic state. Here, we show that the energy transfer among CQDs in a polydispersed ensemble in solution suffices to explain the excess Stokes shift. This energy transfer is primarily due to CQD aggregation and can be substantially eliminated by extreme dilution, higher-viscosity solvent, or better-dispersed colloids. Our findings highlight that ensemble polydispersity remains the primary source of the Stokes shift in CQDs in solution, propagating into the Stokes shift in films and the open-circuit voltage deficit in CQD solar cells. Improved synthetic control can bring notable advancements in CQD photovoltaics, and the Stokes shift continues to provide a sensitive and significant metric to monitor ensemble size distribution.

Colloidal quantum dot solar cells exploiting hierarchical structuring.

Extremely thin-absorber solar cells offer low materials utilization and simplified manufacture but require improved means to enhance photon absorption in the active layer. Here, we report enhanced-absorption colloidal quantum dot (CQD) solar cells that feature transfer-stamped solution-processed pyramid-shaped electrodes employed in a hierarchically structured device. The pyramids increase, by up to a factor of 2, the external quantum efficiency of the device at absorption-limited wavelengths near the absorber band edge. We show that absorption enhancement can be optimized with increased pyramid angle with an appreciable net improvement in power conversion efficiency, that is, with the gain in current associated with improved absorption and extraction overcoming the smaller fractional decrease in open-circuit voltage associated with increased junction area. We show that the hierarchical combination of micron-scale structured electrodes with nanoscale films provides for an optimized enhancement at absorption-limited wavelengths. We fabricate 54.7° pyramid-patterned electrodes, conformally apply the quantum dot films, and report pyramid CQD solar cells that exhibit a 24% improvement in overall short-circuit current density with champion devices providing a power conversion efficiency of 9.2%.

High-Efficiency Colloidal Quantum Dot Photovoltaics via Robust Self-Assembled Monolayers.

The optoelectronic tunability offered by colloidal quantum dots (CQDs) is attractive for photovoltaic applications but demands proper band alignment at electrodes for efficient charge extraction at minimal cost to voltage. With this goal in mind, self-assembled monolayers (SAMs) can be used to modify interface energy levels locally. However, to be effective SAMs must be made robust to treatment using the various solvents and ligands required for to fabricate high quality CQD solids. We report robust self-assembled monolayers (R-SAMs) that enable us to increase the efficiency of CQD photovoltaics. Only by developing a process for secure anchoring of aromatic SAMs, aided by deposition of the SAMs in a water-free deposition environment, were we able to provide an interface modification that was robust against the ensuing chemical treatments needed in the fabrication of CQD solids. The energy alignment at the rectifying interface was tailored by tuning the R-SAM for optimal alignment relative to the CQD quantum-confined electron energy levels. This resulted in a CQD PV record power conversion efficiency (PCE) of 10.7% with enhanced reproducibility relative to controls.

Materials processing routes to trap-free halide perovskites.

Photovoltaic devices based on lead iodide perovskite films have seen rapid advancements, recently achieving an impressive 17.9% certified solar power conversion efficiency. Reports have consistently emphasized that the specific choice of growth conditions and chemical precursors is central to achieving superior performance from these materials; yet the roles and mechanisms underlying the selection of materials processing route is poorly understood. Here we show that films grown under iodine-rich conditions are prone to a high density of deep electronic traps (recombination centers), while the use of a chloride precursor avoids the formation of key defects (Pb atom substituted by I) responsible for short diffusion lengths and poor photovoltaic performance. Furthermore, the lowest-energy surfaces of perovskite crystals are found to be entirely trap-free, preserving both electron and hole delocalization to a remarkable degree, helping to account for explaining the success of polycrystalline perovskite films. We construct perovskite films from I-poor conditions using a lead acetate precursor, and our measurement of a long (600 ± 40 nm) diffusion length confirms this new picture of the importance of growth conditions.

Early Warning for the Electrolyzer: Monitoring CO2 Reduction via In-Line Electrochemical Impedance Spectroscopy.

The electrochemical CO2 reduction reaction (CO2 RR) to fuels and feedstocks presents an opportunity to decarbonize the chemical industry, and current electrolyzer performance levels approach commercial viability. However, stability remains below that required, in part because of the challenge of probing these electrolyzer systems in real time and the challenge of determining the root cause of failure. Failure can result from initial conditions (e. g., the over- or under-compression of the electrolyzer), gradual degradation of components (e. g., cathode or anode catalysts), the accumulation of products or by-products, or immediate changes such as the development of a hole in the membrane or a short circuit. Identifying and mitigating these assembly-related, gradual, and immediate failure modes would increase both electrolyzer lifetime and economic viability of CO2 RR. We demonstrate the continuous monitoring of CO2 RR electrolyzers during operation via non-disruptive, real-time electrochemical impedance spectroscopy (EIS) analysis. Using this technique, we characterise common failure modes - compression, salt formation, and membrane short circuits - and identify electrochemical parameter signatures for each. We further propose a framework to identify, predict, and prevent failures in CO2 RR electrolyzers. This framework allowed for the prediction of anode degradation ~11 hours before other indicators such as selectivity or voltage.

A donor-supply electrode (DSE) for colloidal quantum dot photovoltaics.

The highest-performing colloidal quantum dot (CQD) photovoltaics (PV) reported to date have relied on high-temperature (>500°C) annealing of electron-accepting TiO2. Room-temperature processing reduces energy payback time and manufacturing cost, enables flexible substrates, and permits tandem solar cells that integrate a small-bandgap back cell atop a low-thermal-budget larger-bandgap front cell. Here we report an electrode strategy that enables a depleted-heterojunction CQD PV device to be fabricated entirely at room temperature. We find that simply replacing the high-temperature-processed TiO2 with a sputtered version of the same material leads to poor performance due to the low mobility of the sputtered oxide. We develop instead a two-layer donor-supply electrode (DSE) in which a highly doped, shallow work function layer supplies a high density of free electrons to an ultrathin TiO2 layer via charge-transfer doping. Using the DSE we build all-room-temperature-processed small-bandgap (1 eV) colloidal quantum dot solar cells having 4% solar power conversion efficiency and high fill factor. These 1 eV bandgap cells are suitable for use as the back junction in tandem solar cells. The DSE concept, combined with control over TiO2 stoichiometry in sputtering, provides a much-needed tunable electrode to pair with quantum-size-effect CQD films.

Gold-in-copper at low *CO coverage enables efficient electromethanation of CO2.

The renewable-electricity-powered CO2 electroreduction reaction provides a promising means to store intermittent renewable energy in the form of valuable chemicals and dispatchable fuels. Renewable methane produced using CO2 electroreduction attracts interest due to the established global distribution network; however, present-day efficiencies and activities remain below those required for practical application. Here we exploit the fact that the suppression of *CO dimerization and hydrogen evolution promotes methane selectivity: we reason that the introduction of Au in Cu favors *CO protonation vs. C-C coupling under low *CO coverage and weakens the *H adsorption energy of the surface, leading to a reduction in hydrogen evolution. We construct experimentally a suite of Au-Cu catalysts and control *CO availability by regulating CO2 concentration and reaction rate. This strategy leads to a 1.6× improvement in the methane:H2 selectivity ratio compared to the best prior reports operating above 100 mA cm-2. We as a result achieve a CO2-to-methane Faradaic efficiency (FE) of (56 ± 2)% at a production rate of (112 ± 4) mA cm-2.

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%.

Dopant-tuned stabilization of intermediates promotes electrosynthesis of valuable C3 products.

The upgrading of CO2/CO feedstocks to higher-value chemicals via energy-efficient electrochemical processes enables carbon utilization and renewable energy storage. Substantial progress has been made to improve performance at the cathodic side; whereas less progress has been made on improving anodic electro-oxidation reactions to generate value. Here we report the efficient electroproduction of value-added multi-carbon dimethyl carbonate (DMC) from CO and methanol via oxidative carbonylation. We find that, compared to pure palladium controls, boron-doped palladium (Pd-B) tunes the binding strength of intermediates along this reaction pathway and favors DMC formation. We implement this doping strategy and report the selective electrosynthesis of DMC experimentally. We achieve a DMC Faradaic efficiency of 83 ± 5%, fully a 3x increase in performance compared to the corresponding pure Pd electrocatalyst.

Efficient upgrading of CO to C3 fuel using asymmetric C-C coupling active sites.

The electroreduction of C1 feedgas to high-energy-density fuels provides an attractive avenue to the storage of renewable electricity. Much progress has been made to improve selectivity to C1 and C2 products, however, the selectivity to desirable high-energy-density C3 products remains relatively low. We reason that C3 electrosynthesis relies on a higher-order reaction pathway that requires the formation of multiple carbon-carbon (C-C) bonds, and thus pursue a strategy explicitly designed to couple C2 with C1 intermediates. We develop an approach wherein neighboring copper atoms having distinct electronic structures interact with two adsorbates to catalyze an asymmetric reaction. We achieve a record n-propanol Faradaic efficiency (FE) of (33 ± 1)% with a conversion rate of (4.5 ± 0.1) mA cm-2, and a record n-propanol cathodic energy conversion efficiency (EEcathodic half-cell) of 21%. The FE and EEcathodic half-cell represent a 1.3× improvement relative to previously-published CO-to-n-propanol electroreduction reports.

Infrared Colloidal Quantum Dot Photovoltaics via Coupling Enhancement and Agglomeration Suppression.

Materials optimized for single-junction solar spectral harvesting, such as silicon, perovskites, and large-band-gap colloidal quantum dot solids, fail to absorb the considerable infrared spectral energy that lies below their respective band gap. Here we explore through modeling and experiment the potential for colloidal quantum dots (CQDs) to augment the performance of solar cells by harnessing transmitted light in the infrared. Through detailed balance modeling, we identify the CQD band gap that is best able to augment wafer-based, thin-film, and also solution-processed photovoltaic (PV) materials. The required quantum dots, with an excitonic peak at 1.3 µm, have not previously been studied in depth for solar performance. Using computational studies we find that a new ligand scheme distinct from that employed in better-explored 0.95 µm band gap PbS CQDs is necessary; only via the solution-phase application of a short bromothiol can we prevent dot fusion during ensuing solid-state film treatments and simultaneously offer a high valence band-edge density of states to enhance hole transport. Photoluminescence spectra and transient studies confirm the desired narrowed emission peaks and reduced surface-trap-associated decay. Electronic characterization reveals that only through the use of the bromothiol ligands is strong hole transport retained. The films, when used to make PV devices, achieve the highest AM1.5 power conversion efficiency yet reported in a solution-processed material having a sub-1 eV band gap.

All-Quantum-Dot Infrared Light-Emitting Diodes.

Colloidal quantum dots (CQDs) are promising candidates for infrared electroluminescent devices. To date, CQD-based light-emitting diodes (LEDs) have employed a CQD emission layer sandwiched between carrier transport layers built using organic materials and inorganic oxides. Herein, we report the infrared LEDs that use quantum-tuned materials for each of the hole-transporting, the electron-transporting, and the light-emitting layers. We successfully tailor the bandgap and band position of each CQD-based component to produce electroluminescent devices that exhibit emission that we tune from 1220 to 1622 nm. Devices emitting at 1350 nm achieve peak external quantum efficiency up to 1.6% with a low turn-on voltage of 1.2 V, surpassing previously reported all-inorganic CQD LEDs.

Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes.

Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite-PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI3(-) antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solar cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour.

Engineering colloidal quantum dot solids within and beyond the mobility-invariant regime.

Colloidal quantum dots are attractive materials for efficient, low-cost and facile implementation of solution-processed optoelectronic devices. Despite impressive mobilities (1-30 cm2 V(-1) s(-1)) reported for new classes of quantum dot solids, it is--surprisingly--the much lower-mobility (10(-3)-10(-2) cm2 V(-1) s(-1)) solids that have produced the best photovoltaic performance. Here we show that it is not mobility, but instead the average spacing among recombination centres that governs the diffusion length of charges in today's quantum dot solids. In this regime, colloidal quantum dot films do not benefit from further improvements in charge carrier mobility. We develop a device model that accurately predicts the thickness dependence and diffusion length dependence of devices. Direct diffusion length measurements suggest the solid-state ligand exchange procedure as a potential origin of the detrimental recombination centres. We then present a novel avenue for in-solution passivation with tightly bound chlorothiols that retain passivation from solution to film, achieving an 8.5% power conversion efficiency.

The complete in-gap electronic structure of colloidal quantum dot solids and its correlation with electronic transport and photovoltaic performance.

The direct observation of the complete electronic band structure of a family of PbS CQD solids via photoelectron spectroscopy is reported. We investigate how materials processing strategies, such as the latest passivation methods that produce record-performance photovoltaics, achieve their performance advances. Halide passivated films show a drastic reduction in states in the midgap, contributing to a marked improvement in the device performance.

Role of bond adaptability in the passivation of colloidal quantum dot solids.

Colloidal quantum dot (CQD) solids are attractive materials for photovoltaic devices due to their low-cost solution-phase processing, high absorption cross sections, and their band gap tunability via the quantum size effect. Recent advances in CQD solar cell performance have relied on new surface passivation strategies. Specifically, cadmium cation passivation of surface chalcogen sites in PbS CQDs has been shown to contribute to lowered trap state densities and improved photovoltaic performance. Here we deploy a generalized solution-phase passivation strategy as a means to improving CQD surface management. We connect the effects of the choice of metal cation on solution-phase surface passivation, film-phase trap density of states, minority carrier mobility, and photovoltaic power conversion efficiency. We show that trap passivation and midgap density of states determine photovoltaic device performance and are strongly influenced by the choice of metal cation. Supported by density functional theory simulations, we propose a model for the role of cations, a picture wherein metals offering the shallowest electron affinities and the greatest adaptability in surface bonding configurations eliminate both deep and shallow traps effectively even in submonolayer amounts. This work illustrates the importance of materials choice in designing a flexible passivation strategy for optimum CQD device performance.

Ordered nanopillar structured electrodes for depleted bulk heterojunction colloidal quantum dot solar cells.

A bulk heterojunction of ordered titania nanopillars and PbS colloidal quantum dots is developed. By using a pre-patterned template, an ordered titania nanopillar matrix with nearest neighbours 275 nm apart and height of 300 nm is fabricated and subsequently filled in with PbS colloidal quantum dots to form an ordered depleted bulk heterojunction exhibiting power conversion efficiency of 5.6%.