Rational Design of Local Reaction Environment for Electrocatalytic Conversion of CO2 into Multicarbon Products.

The electrocatalytic conversion of CO2 into multi-carbon (C2+) products provides an attractive route for storing intermittent renewable electricity as fuels and feedstocks with high energy densities. Although substantial progress has been made in selective electrosynthesis of C2+ products via engineering the catalyst, rational design of the local reaction environment in the vicinity of catalyst surface also acts as an effective approach for further enhancing the performance. Here, we discuss recent advances and pertinent challenges in the modulation of local reaction environment, encompassing local pH, the choice of the species and concentrations of cations and anions as well as local reactant/intermediate concentrations, for achieving high C2+ selectivity. In addition, mechanistic understanding in the effects of the local reaction environment is also discussed. Particularly, the important progress extracted from in situ and operando spectroscopy techniques provides insights into how local reaction environment affects C-C coupling and key intermediates formation that lead to reaction pathways toward a desired C2+ product. The possible future direction in understanding and engineering the local reaction environment is also provided.

Preventing Alloy Electrocatalyst Segregation in Air Using Sacrificial Passivating Overlayers.

Many alloy electrocatalysts, including intermetallics, are exceptionally sensitive to segregation in air due to the electronic dissimilarity of the constituent metals. We demonstrate that even alloys with strong cohesive energies rapidly segregate upon air exposure, completely burying the less reactive constituent metal beneath the surface. To circumvent this issue, we develop and validate a new experimental approach for bridging the pressure gap between electronic structure characterization performed under ultrahigh vacuum and electrocatalytic activity testing performed under ambient conditions. This method is based on encapsulation of the alloy surface with a sacrificial passivating overlayer of aluminum oxide. These passivating overlayers protect the underlying material from segregation in the air and can be completely and rapidly removed in an alkaline electrochemical environment under potential control. We demonstrate that alloy surfaces prepared, protected, and introduced into the electrolyte in this manner exhibit near-surface compositions consistent with those of the bulk material despite prior air exposure. We also demonstrate that this protection scheme does not alter the electrocatalytic activity of benchmark electrocatalysts. Implementation of this approach will enable reliable correlations between the electrocatalytic activity measured under ambient conditions and the near-surface electronic structure measured under ultrahigh vacuum.

Unraveling the rate-determining step of C2+ products during electrochemical CO reduction.

The electrochemical reduction of CO has drawn a large amount of attention due to its potential to produce sustainable fuels and chemicals by using renewable energy. However, the reaction's mechanism is not yet well understood. A major debate is whether the rate-determining step for the generation of multi-carbon products is C-C coupling or CO hydrogenation. This paper conducts an experimental analysis of the rate-determining step, exploring pH dependency, kinetic isotope effects, and the impact of CO partial pressure on multi-carbon product activity. Results reveal constant multi-carbon product activity with pH or electrolyte deuteration changes, and CO partial pressure data aligns with the theoretical formula derived from *CO-*CO coupling as the rate-determining step. These findings establish the dimerization of two *CO as the rate-determining step for multi-carbon product formation. Extending the study to commercial copper nanoparticles and oxide-derived copper catalysts shows their rate-determining step also involves *CO-*CO coupling. This investigation provides vital kinetic data and a theoretical foundation for enhancing multi-carbon product production.

Impact of Anodic Oxidation Reactions in the Performance Evaluation of High-Rate CO2 /CO Electrolysis.

The membrane-electrode assembly (MEA) approach appears to be the most promising technique to realize the high-rate CO2 /CO electrolysis, however there are major challenges related to the crossover of ions and liquid products from cathode to anode via the membrane and the concomitant anodic oxidation reactions (AORs). In this perspective, by combining experimental and theoretical analyses, several impacts of anodic oxidation of liquid products in terms of performance evaluation are investigated. First, the crossover behavior of several typical liquid products through an anion-exchange membrane is analyzed. Subsequently, two instructive examples (introducing formate or ethanol oxidation during electrolysis) reveals that the dynamic change of the anolyte (i.e., pH and composition) not only brings a slight shift of anodic potentials (i.e., change of competing reactions), but also affects the chemical stability of the anode catalyst. Anodic oxidation of liquid products can also cause either over- or under-estimation of the Faradaic efficiency, leading to an inaccurate assessment of overall performance. To comprehensively understand fundamentals of AORs, a theoretical guideline with hierarchical indicators is further developed to predict and regulate the possible AORs in an electrolyzer. The perspective concludes by giving some suggestions on rigorous performance evaluations for high-rate CO2 /CO electrolysis in an MEA-based setup.

Tuning Surface Reactivity and Electric Field Strength via Intermetallic Alloying.

Many electrosynthesis reactions, such as CO2 reduction to multicarbon products, involve the formation of dipolar and polarizable transition states during the rate-determining step. Systematic and independent control over surface reactivity and electric field strength would accelerate the discovery of highly active electrocatalysts for these reactions by providing a means of reducing the transition state energy through field stabilization. Herein, we demonstrate that intermetallic alloying enables independent and systematic control over d-band energetics and work function through the variation of alloy composition and oxophilic constituent identity, respectively. We identify several intermetallic phases exhibiting properties that should collectively yield higher intrinsic activity for CO reduction compared to conventional Cu-based electrocatalysts. However, we also highlight the propensity of these alloys to segregate in air as a significant roadblock to investigating their electrocatalytic activity.

Influence of Headgroups in Ethylene-Tetrafluoroethylene-Based Radiation-Grafted Anion Exchange Membranes for CO2 Electrolysis.

The performance of zero-gap CO2 electrolysis (CO2E) is significantly influenced by the membrane's chemical structure and physical properties due to its effects on the local reaction environment and water/ion transport. Radiation-grafted anion-exchange membranes (RG-AEM) have demonstrated high ionic conductivity and durability, making them a promising alternative for CO2E. These membranes were fabricated using two different thicknesses of ethylene-tetrafluoroethylene polymer substrates (25 and 50 µm) and three different headgroup chemistries: benzyl-trimethylammonium, benzyl-N-methylpyrrolidinium, and benzyl-N-methylpiperidinium (MPIP). Our membrane characterization and testing in zero-gap cells over Ag electrocatalysts under commercially relevant conditions showed correlations between the water uptake, ionic conductivity, hydration, and cationic-head groups with the CO2E efficiency. The thinner 25 µm-based AEM with the MPIP-headgroup (ion-exchange capacities of 2.1 ± 0.1 mmol g-1) provided balanced in situ test characteristics with lower cell potentials, high CO selectivity, reduced liquid product crossover, and enhanced water management while maintaining stable operation compared to the commercial AEMs. The CO2 electrolyzer with an MPIP-AEM operated for over 200 h at 150 mA cm-2 with CO selectivities up to 80% and low cell potentials (around 3.1 V) while also demonstrating high conductivities and chemical stability during performance at elevated temperatures (above 60 °C).

Enriching Surface-Accessible CO2 in the Zero-Gap Anion-Exchange-Membrane-Based CO2 Electrolyzer.

Zero-gap anion exchange membrane (AEM)-based CO2 electrolysis is a promising technology for CO production, however, their performance at elevated current densities still suffers from the low local CO2 concentration due to heavy CO2 neutralization. Herein, via modulating the CO2 feed mode and quantitative analyzing CO2 utilization with the aid of mass transport modeling, we develop a descriptor denoted as the surface-accessible CO2 concentration ([CO2 ]SA ), which enables us to indicate the transient state of the local [CO2 ]/[OH- ] ratio and helps define the limits of CO2 -to-CO conversion. To enrich the [CO2 ]SA , we developed three general strategies: (1) increasing catalyst layer thickness, (2) elevating CO2 pressure, and (3) applying a pulsed electrochemical (PE) method. Notably, an optimized PE method allows to keep the [CO2 ]SA at a high level by utilizing the dynamic balance period of CO2 neutralization. A maximum jCO of 368±28 mA cmgeo -2 was achieved using a commercial silver catalyst.

Unraveling the rate-limiting step of two-electron transfer electrochemical reduction of carbon dioxide.

Electrochemical reduction of CO2 (CO2ER) has received significant attention due to its potential to sustainably produce valuable fuels and chemicals. However, the reaction mechanism is still not well understood. One vital debate is whether the rate-limiting step (RLS) is dominated by the availability of protons, the conversion of water molecules, or the adsorption of CO2. This paper describes insights into the RLS by investigating pH dependency and kinetic isotope effect with respect to the rate expression of CO2ER. Focusing on electrocatalysts geared towards two-electron transfer reactions, we find the generation rates of CO and formate to be invariant with either pH or deuteration of the electrolyte over Au, Ag, Sn, and In. We elucidate the RLS of two-electron transfer CO2ER to be the adsorption of CO2 onto the surface of electrocatalysts. We expect this finding to provide guidance for improving CO2ER activity through the enhancement of the CO2 adsorption processes by strategies such as surface modification of catalysts as well as careful control of pressure and interfacial electric field within reactors.

Investigation of Ethylene and Propylene Production from CO2 Reduction over Copper Nanocubes in an MEA-Type Electrolyzer.

Previous work carried out in fully liquid environments and at low current densities has demonstrated that highly uniform faceted copper nanocrystals display different selectivity profiles in CO2 reduction compared to polycrystalline copper. As part of ongoing upscaling efforts, it is a matter of interest to investigate whether the high selectivity toward ethylene of copper nanocubes, which show a preferential (100) orientation, is maintained in gas-fed electrolyzers, thus enabling the energy-efficient production of this valuable commodity chemical at industrially relevant current densities. In this work, we assessed the electrochemical CO2 reduction reaction performance of highly uniform copper nanocubes loaded onto gas diffusion electrodes (GDEs) in a zero-gap device. The copper nanocube-loaded GDEs maintained high Faradaic efficiencies toward ethylene at elevated total current densities, resulting in higher overall partial current densities toward this product compared to benchmark electrodes. Interestingly, CO2 reduction to propylene, albeit with low partial current densities, was also observed. However, double-layer capacitance measurements revealed that the performance observed at high current densities is significantly influenced by electrode flooding. The findings of this study can inform future efforts geared toward optimizing the electrodes with this promising class of catalysts.

In Situ Analysis of the Facets of Cu-Based Electrocatalysts in Alkaline Media Using Pb Underpotential Deposition.

Establishing relationships between the surface atomic structure and activity of Cu-based electrocatalysts for CO2 and CO reduction is hindered by probable surface restructuring under working conditions. Insights into these structural evolutions are scarce as techniques for monitoring the surface facets in conventional experimental designs are lacking. To directly correlate surface reconstructions to changes in selectivity or activity, the development of surface-sensitive, electrochemical probes is highly desirable. Here, we report the underpotential deposition of lead over three low index Cu single crystals in alkaline media, the preferred electrolyte for CO reduction studies. We find that underpotential deposition of Pb onto these facets occurs at distinct potentials, and we use these benchmarks to probe the predominant facet of polycrystalline Cu electrodes in situ. Finally, we demonstrate that Cu and Pb form an irreversible surface alloy during underpotential deposition, which limits this method to investigating the surface atomic structure after reaction.

How to extract adsorption energies, adsorbate-adsorbate interaction parameters and saturation coverages from temperature programmed desorption experiments.

We present a scheme to extract the adsorption energy, adsorbate interaction parameter and the saturation coverage from temperature programmed desorption (TPD) experiments. We propose that the coverage dependent adsorption energy can be fit using a functional form including the configurational entropy and linear adsorbate-adsorbate interaction terms. As one example of this scheme, we analyze TPD of CO desorption on Au(211) and Au(310) surfaces. We determine that under atmospheric CO pressure, the steps of both facets adsorb between 0.4-0.9 ML coverage of CO*. We compare this result against energies obtained from five density functionals, RPBE, PBE, PBE-D3, RPBE-D3 and BEEF-vdW. We find that the energies and equilibrium coverages from RPBE-D3 and PBE are closest to the values determined from the TPD.

Role of ion-selective membranes in the carbon balance for CO2 electroreduction via gas diffusion electrode reactor designs.

In this work, the effect of ion-selective membranes on the detailed carbon balance was systematically analyzed for high-rate CO2 reduction in GDE-type flow electrolyzers. By using different ion-selective membranes, we show nearly identical catalytic selectivity for CO2 reduction, which is primarily due to a similar local reaction environment created at the cathode/electrolyte interface via the introduction of a catholyte layer. In addition, based on a systematic exploration of gases released from electrolytes and the dynamic change of electrolyte speciation, we demonstrate the explicit discrepancy in carbon balance paths for the captured CO2 at the cathode/catholyte interface via reaction with OH- when using different ion-selective membranes: (i) the captured CO2 could be transported through an anion exchange membrane in the form of CO3 2-, subsequently releasing CO2 along with O2 in the anolyte, and (ii) with a cation exchange membrane, the captured CO2 would be accumulated in the catholyte in the form of CO3 2-, while (iii) with the use of a bipolar membrane, the captured CO2 could be released at the catholyte/membrane interface in the form of gaseous CO2. The unique carbon balance path for each type of membrane is linked to ion species transported through the membranes.

Analysis of Mass Flows and Membrane Cross-over in CO2 Reduction at High Current Densities in an MEA-Type Electrolyzer.

Cell designs that integrate membrane-electrode assemblies (MEAs) with highly selective catalysts are a promising route to reduce ohmic losses and achieve high energy efficiency in CO2 reduction at industrially relevant current densities. In this work, porous silver filtration membranes are demonstrated as simple and efficient gas-diffusion electrodes for CO2 reduction to CO at high current densities in an MEA-type device. A partial current density for CO of up to ca. 200 mA cm-2 was achieved at a cell voltage of ca. 3.3 V, in tandem with minimal H2 production. However, the analysis of cathodic and anodic outlet streams revealed that CO2 cross-over across the anion-exchange membranes, mostly in the form of CO32- but partially as HCOO- generated over the cathode, actually exceeds the amount of CO2 converted to the target product, resulting in a poor utilization of the reactant and in the early onset of mass transfer limitations. In addition, CO2 cross-over leads to a nonstoichiometric decrease of the outlet flow rate from the cathodic compartment. This effect can lead to a substantial overestimation of catalytic performance if the inlet flow rate of CO2 is used as reference for calculating partial current densities and Faradaic efficiencies. The results of this work highlight the importance of carrying out a carbon balance, in addition to traditional measurements of activity and selectivity, to adequately assess the performance of CO2 reduction devices at high current densities, and inform future efforts aimed at mitigating membrane cross-over in MEA-type electrolyzers for CO2 reduction.

Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte.

To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcohols, such as ethylene and ethanol, from electrochemical CO2 reduction (CO2R). There are variety of factors that impact CO2R activity and selectivity, including the catalyst surface structure, morphology, composition, the choice of electrolyte ions and pH, and the electrochemical cell design. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO2R catalysis on Cu, with the purpose of providing new insights, critical evaluations, and guidance to the field with regard to research directions and best practices. First, we describe the various experimental probes and complementary theoretical methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO2R on Cu. We then analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochemical CO2R.

Structure Sensitivity in the Electrocatalytic Reduction of CO2 with Gold Catalysts.

An understanding of the influence of structural surface features on electrocatalytic reactions is vital for the development of efficient nanostructured catalysts. Gold is the most active and selective known electrocatalyst for the reduction of CO2 to CO in aqueous electrolytes. Numerous strategies have been proposed to improve its intrinsic activity. Nonetheless, the atomistic knowledge of the nature of the active sites remains elusive. We systematically investigated the structure sensitivity of Au single crystals for electrocatalytic CO2 reduction. Reaction kinetics for the formation of CO are strongly dependent on the surface structure. Under-coordinated sites, such as those present in Au(110) and at the steps of Au(211), show at least 20-fold higher activity than more coordinated configurations (for example, Au(100)). By selectively poisoning under-coordinated sites with Pb, we have confirmed that these are the active sites for CO2 reduction.

Strategies for stable water splitting via protected photoelectrodes.

Photoelectrochemical (PEC) solar-fuel conversion is a promising approach to provide clean and storable fuel (e.g., hydrogen and methanol) directly from sunlight, water and CO2. However, major challenges still have to be overcome before commercialization can be achieved. One of the largest barriers to overcome is to achieve a stable PEC reaction in either strongly basic or acidic electrolytes without degradation of the semiconductor photoelectrodes. In this work, we discuss fundamental aspects of protection strategies for achieving stable solid/liquid interfaces. We then analyse the charge transfer mechanism through the protection layers for both photoanodes and photocathodes. In addition, we review protection layer approaches and their stabilities for a wide variety of experimental photoelectrodes for water reduction. Finally, we discuss key aspects which should be addressed in continued work on realizing stable and practical PEC solar water splitting systems.

Integrating a dual-silicon photoelectrochemical cell into a redox flow battery for unassisted photocharging.

Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient photoelectrochemical reactions. Here we report an efficient SRFC based on a dual-silicon photoelectrochemical cell and a quinone/bromine redox flow battery for in situ solar energy conversion and storage. Using narrow bandgap silicon for efficient photon collection and fast redox couples for rapid interface charge injection, our device shows an optimal solar-to-chemical conversion efficiency of ∼5.9% and an overall photon-chemical-electricity energy conversion efficiency of ∼3.2%, which, to our knowledge, outperforms previously reported SRFCs. The proposed SRFC can be self-photocharged to 0.8 V and delivers a discharge capacity of 730 mAh l(-1). Our work may guide future designs for highly efficient solar rechargeable devices.

Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation.

The past 10 years have seen great advances in the field of electrochemical hydrogen evolution. In particular, several new nonprecious metal electrocatalysts, for example, the MoS2 or the Ni2P family of materials, have emerged as contenders for electrochemical hydrogen evolution under harsh acidic conditions offering nearly platinum-like catalytic performance. The developments have been particularly fast in the last 5 years, and the present Perspective highlights key developments and discusses them, along with hydrogen evolution in general, in the context of the global energy problem.

Comparison of the Performance of CoP-Coated and Pt-Coated Radial Junction n(+)p-Silicon Microwire-Array Photocathodes for the Sunlight-Driven Reduction of Water to H2(g).

The electrocatalytic performance for hydrogen evolution has been evaluated for radial-junction n(+)p-Si microwire (MW) arrays with Pt or cobalt phosphide, CoP, nanoparticulate catalysts in contact with 0.50 M H2SO4(aq). The CoP-coated (2.0 mg cm(-2)) n(+)p-Si MW photocathodes were stable for over 12 h of continuous operation and produced an open-circuit photovoltage (Voc) of 0.48 V, a light-limited photocurrent density (Jph) of 17 mA cm(-2), a fill factor (ff) of 0.24, and an ideal regenerative cell efficiency (ηIRC) of 1.9% under simulated 1 Sun illumination. Pt-coated (0.5 mg cm(-2)) n(+)p-Si MW-array photocathodes produced Voc = 0.44 V, Jph = 14 mA cm(-2), ff = 0.46, and η = 2.9% under identical conditions. Thus, the MW geometry allows the fabrication of photocathodes entirely comprised of earth-abundant materials that exhibit performance comparable to that of devices that contain Pt.