Key Role of Cations in Stabilizing Hydrogen Radicals for CO2-to-CO Conversion via a Reverse Water-Gas Shift Reaction.

Electrochemically converting CO2 into valuable chemicals and fuels in acidic media is argued as a promising energy- and carbon-efficient route. Although several key roles of alkali cations have been unveiled, the alkali cation trends for CO2 reduction remain largely elusive. With decreasing cation size from Cs+ to Li+, here we show that the apparent proton diffusion coefficient in 3.0 M Li+ is tens-fold lower than in 3.0 M K+ and 3.0 M Cs+ acidic electrolytes. Although Li+ has the strongest inhibition ability for proton transport, it acts the worst for both the CO2-to-CO conversion and partial current density on Au catalysts. Unexpectedly, K+ with a higher proton transport performs the best for CO2-to-CO conversion. We thus revisit the roles of alkali cations and find that hydrated K+ can stabilize hydrogen radicals benefiting CO2 conversion at the electrode interface while for Li+ this is not the case. This study proposes that cation-stabilized atomic hydrogen assists in activating CO2 via a reverse water-gas shift route under electrochemical conditions.

Steering the Reconstruction of Oxide-Derived Cu by Secondary Metal for Electrosynthesis of n-Propanol from CO.

As fuel and an important chemical feedstock, n-propanol is highly desired in electrochemical CO2/CO reduction on Cu catalysts. However, the precise regulation of the Cu localized structure is still challenging and poorly understood, thus hindering the selective n-propanol electrosynthesis. Herein, by decorating Au nanoparticles (NPs) on CuO nanosheets (NSs), we present a counterintuitive transformation of CuO into undercoordinated Cu sites locally around Au NPs during CO reduction. In situ spectroscopic techniques reveal the Au-steered formation of abundant undercoordinated Cu sites during the removal of oxygen on CuO. First-principles accuracy molecular dynamic simulation demonstrates that the localized Cu atoms around Au tend to rearrange into disordered layer rather than a Cu (111) close-packed plane observed on bare CuO NSs. These Au-steered undercoordinated Cu sites facilitate CO binding, enabling selective electroreduction of CO into n-propanol with a high Faradaic efficiency of 48% in a flow cell. This work provides new insight into the regulation of the oxide-derived catalysts reconstruction with a secondary metal component.

Electrochemical Redox Conversion of Formate to CO via Coupling Fe-Co Layered Double Hydroxides and Au Catalysts.

Formate has been considered an inactive molecule and thus cannot be further reduced under CO2 reduction conditions, which limits its widespread application as feedstock. Here we present an electrochemical redox conversion of formate to CO through the potential-dependent generation of carbon dioxide radical anions (CO2 ⋅- ) on Fe-Co layered double hydroxides (Fe-Co LDHs) and the subsequent reduction of CO2 ⋅- to CO on Au catalysts. We present an electrodeposition protocol for the synthesis of Fe-Co LDHs with precise composition control and find that Fe1 Co4 exhibits a promising potential window for CO2 ⋅- formation between 1.14 and 1.4 V and an optimized potential at 1.24 V at a neutral pH condition. We further determined the formation of CO2 ⋅- at 1.24 V via electron paramagnetic resonance and CO2 at >1.4 V through differential electrochemical mass spectrometry. This work provides a redox chemistry route for converting formate into CO through a coupled slit parallel-plate electrode system.

Electron Paramagnetic Resonance Tracks Condition-Sensitive Water Radical Cation.

Oxidizing species or radicals generated in water are of vital importance in catalysis, the environment, and biology. In addition to several related reactive oxygen species, using electron paramagnetic resonance (EPR), we present a nontrapping chemical transformation pathway to track water radical cation (H2O+•) species, whose formation is very sensitive to the conditioning environments, such as light irradiation, mechanical action, and gas/chemical introduction. We reveal that H2O+• can oxidize the 5,5-dimethyl-1-pyrroline N-oxide (DMPO) to the crucial epoxy hydroxylamine (HDMP=O) intermediate, which further reacts with the hydroxyl radical (•OH) for the formation of the EPR-active sextet radical (DMPO=O•). Interestingly, we uncover that H2O+• can react with dimethyl methylphosphonate (DMMP), 2-methyl-2-nitrosopropane (MNP), 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide (BMPO), and α-phenyl-N-tert-butylnitrone (PBN) which contain a double-bond structure to produce corresponding derivatives as well. It is thus expected that both H2O+• and •OH are ubiquitous in nature and in various water-containing experimental systems. These findings provide a novel perspective on radicals for water redox chemistry.

Criteria for Efficient Photocatalytic Water Splitting Revealed by Studying Carrier Dynamics in a Model Al-doped SrTiO3 Photocatalyst.

Overall water splitting (OWS) using semiconductor photocatalysts is a promising method for solar fuel production. Achieving a high quantum efficiency is one of the most important prerequisites for photocatalysts to realize high solar-to-fuel efficiency. In a recent study (Nature 2020, 58, 411-414), a quantum efficiency of almost 100 % has been achieved in an aluminum-doped strontium titanate (SrTiO3 : Al) photocatalyst. Herein, using the SrTiO3 : Al as a model photocatalyst, we reveal the criteria for efficient photocatalytic water splitting by investigating the carrier dynamics through a comprehensive photoluminescence study. It is found that the Al doping suppresses the generation of Ti3+ recombination centers in SrTiO3 , the surface band bending facilitates charge separation, and the in situ photo-deposited Rh/Cr2 O3 and CoOOH co-catalysts render efficient charge extraction. By suppressing photocarrier recombination and establishing a facile charge separation and extraction mechanism, high quantum efficiency can be achieved even on photocatalysts with a very short (sub-ns) intrinsic photocarrier lifetime, challenging the belief that a long carrier lifetime is a fundamental requirement. Our findings could provide guidance on the design of OWS photocatalysts toward more efficient solar-to-fuel conversion.

Self-adaptive amorphous CoOxCly electrocatalyst for sustainable chlorine evolution in acidic brine.

Electrochemical chlorine evolution reaction is of central importance in the chlor-alkali industry, but the chlorine evolution anode is largely limited by water oxidation side reaction and corrosion-induced performance decay in strong acids. Here we present an amorphous CoOxCly catalyst that has been deposited in situ in an acidic saline electrolyte containing Co2+ and Cl- ions to adapt to the given electrochemical condition and exhibits ~100% chlorine evolution selectivity with an overpotential of ~0.1 V at 10 mA cm-2 and high stability over 500 h. In situ spectroscopic studies and theoretical calculations reveal that the electrochemical introduction of Cl- prevents the Co sites from charging to a higher oxidation state thus suppressing the O-O bond formation for oxygen evolution. Consequently, the chlorine evolution selectivity has been enhanced on the Cl-constrained Co-O* sites via the Volmer-Heyrovsky pathway. This study provides fundamental insights into how the reactant Cl- itself can work as a promoter toward enhancing chlorine evolution in acidic brine.

Cu+-Mediated CO Coordination for Promoting C-C Coupling for CO2 and CO Electroreduction.

Selective electrochemical upgrading of CO2 to multicarbon (C2+) products requires a C-C coupling process, yet the underlying promoting mechanism of widely involved Cu oxidation states remains largely unclear, hindering the subtle design of efficient catalysts. Herein, we unveil the critical role of Cu+ in promoting C-C coupling via coordination with a CO intermediate during electrochemical CO2 reduction. We find that, relative to other halogen anions, iodide (I-) in HCO3- electrolytes accelerates the generation of strongly oxidative hydroxyl radicals that accounts for the formation of Cu+, which can be dynamically stabilized by I- via the formation of CuI. The in situ generated CO intermediate strongly binds to CuI sites, forming nonclassical Cu(CO)n+ complexes, leading to an approximately 3.0-fold increase of C2+ Faradaic efficiency at -0.9 VRHE relative to that of I--free Cu surfaces. Accordingly, a deliberate introduction of CuI into I--containing HCO3- electrolytes for direct CO electroreduction brings about a 4.3-fold higher C2+ selectivity. This work provides insights into the role of Cu+ in C-C coupling and the enhanced C2+ selectivity for CO2 and CO electrochemical reduction.

Non-covalent ligand-oxide interaction promotes oxygen evolution.

Strategies to generate high-valence metal species capable of oxidizing water often employ composition and coordination tuning of oxide-based catalysts, where strong covalent interactions with metal sites are crucial. However, it remains unexplored whether a relatively weak "non-bonding" interaction between ligands and oxides can mediate the electronic states of metal sites in oxides. Here we present an unusual non-covalent phenanthroline-CoO2 interaction that substantially elevates the population of Co4+ sites for improved water oxidation. We find that phenanthroline only coordinates with Co2+ forming soluble Co(phenanthroline)2(OH)2 complex in alkaline electrolytes, which can be deposited as amorphous CoOxHy film containing non-bonding phenanthroline upon oxidation of Co2+ to Co3+/4+. This in situ deposited catalyst demonstrates a low overpotential of 216 mV at 10 mA cm-2 and sustainable activity over 1600 h with Faradaic efficiency above 97%. Density functional theory calculations reveal that the presence of phenanthroline can stabilize CoO2 through the non-covalent interaction and generate polaron-like electronic states at the Co-Co center.

Hydroxyl radicals dominate reoxidation of oxide-derived Cu in electrochemical CO2 reduction.

Cuδ+ sites on the surface of oxide-derived copper (OD-Cu) are of vital importance in electrochemical CO2 reduction reaction (CO2RR). However, the underlying reason for the dynamically existing Cuδ+ species, although thermodynamically unstable under reductive CO2RR conditions, remains uncovered. Here, by using electron paramagnetic resonance, we identify the highly oxidative hydroxyl radicals (OH•) formed at room temperature in HCO3- solutions. In combination with in situ Raman spectroscopy, secondary ion mass spectrometry, and isotope-labelling, we demonstrate a dynamic reduction/reoxidation behavior at the surface of OD-Cu and reveal that the fast oxygen exchange between HCO3- and H2O provides oxygen sources for the formation of OH• radicals. In addition, their continuous generations can cause spontaneous oxidation of Cu electrodes and produce surface CuOx species. Significantly, this work suggests that there is a "seesaw-effect" between the cathodic reduction and the OH•-induced reoxidation, determining the chemical state and content of Cuδ+ species in CO2RR. This insight is supposed to thrust an understanding of the crucial role of electrolytes in CO2RR.

Efficient Alkaline Water Oxidation with a Regenerable Nickel Pseudo-Complex.

Efficient and robust electrocatalysts are required for the oxygen evolution reaction (OER). Photosystem II-inspired synthetic transition metal complexes have shown promising OER activity in water-poor or mild conditions, yet challenges remain in the improvement of current density and performance stability for practical applications in alkaline electrolytes in contrast to solid-state oxide catalysts. Here, we report that a nickel pseudo-complex (bpy)zNiOxHy (bpy = 2,2'-bipyridine) catalyst, which bridges solid oxide and molecular catalysts, exhibits the highest OER activity among nickel-based catalysts with a turnover frequency of 1.1 s-1 at an overpotential of 0.30 volts, even outperforming iron-incorporated nickel (oxy)hydroxide under an identical nickel mass load. Benefiting from the strong coordination between bpy and nickel, this (bpy)zNiOxHy catalyst exhibits long-term stability in highly alkaline media at 1.0 mA cm-2 for over 200 h and at 20 mA cm-2 for over 60 h. Our findings indicate that dynamically coordinating a small amount of bpy in the catalyst layer efficiently sustains highly active nickel sites for water oxidation, demonstrating a general strategy for improving the activity of transition metal sites with active ligands beyond the incorporation of metal cations to form double-layered hydroxides.

A self-healing catalyst for electrocatalytic and photoelectrochemical oxygen evolution in highly alkaline conditions.

While self-healing is considered a promising strategy to achieve long-term stability for oxygen evolution reaction (OER) catalysts, this strategy remains a challenge for OER catalysts working in highly alkaline conditions. The self-healing of the OER-active nickel iron layered double hydroxides (NiFe-LDH) has not been successful due to irreversible leaching of Fe catalytic centers. Here, we investigate the introduction of cobalt (Co) into the NiFe-LDH as a promoter for in situ Fe redeposition. An active borate-intercalated NiCoFe-LDH catalyst is synthesized using electrodeposition and shows no degradation after OER tests at 10 mA cm-2 at pH 14 for 1000 h, demonstrating its self-healing ability under harsh OER conditions. Importantly, the presence of both ferrous ions and borate ions in the electrolyte is found to be crucial to the catalyst's self-healing. Furthermore, the implementation of this catalyst in photoelectrochemical devices is demonstrated with an integrated silicon photoanode. The self-healing mechanism leads to a self-limiting catalyst thickness, which is ideal for integration with photoelectrodes since redeposition is not accompanied by increased parasitic light absorption.

Improved water oxidation with metal oxide catalysts via a regenerable and redox-inactive ZnOxHy overlayer.

We report a regenerable and redox-inactive ZnOxHy layer that was in situ deposited onto metal oxides MOz (M = Co, Fe, and Ni) in alkaline media containing [Zn(OH)4]2- species during water oxidation. An interface dipole was developed at the MOz/Zn interface, resulting in a decrease of the OER overpotential. Exemplified by the CoOz/ZnOxHy bilayer structure, it presented a 155 mV lower overpotential to deliver 10 mA cm-2 and long-term stability relative to the unmodified CoOz film.

Phase-Segregated SrCo0.8Fe0.5-xO3-δ/FexOy Heterostructured Catalyst Promotes Alkaline Oxygen Evolution Reaction.

Perovskite oxide is a promising alternative to noble metal electrocatalysts for the oxygen evolution reaction (OER). However, as one of the most active oxide catalysts, cubic SrCoO3 presents poor OER performance relative to the theoretically predicted activity. Appropriate introduction of a guest component in the lattice and surface could largely promote the OER activity. Herein, we present a thermal-induced phase-segregation strategy to synthesize a heterostructured SrCo0.8Fe0.5-xO3-δ/FexOy (SC8F5) catalyst for OER. This novel perovskite/Fe3O4 heterostructure allows us to enhance the electrical conductivity ability, increase the Co oxidation state, and activate the surface oxygen to active oxygen species (O22-/O-) for efficient OER. In contrast to the poor stability of SrCo0.8Fe0.2O3-δ, we found that the SC8F5 heterostructure with segregated Fe3O4 on the surface can mitigate surface reconstruction and stabilize the catalyst structure, thereby increasing catalytic stability.

Highly Dispersed Mo Sites on Pd Nanosheets Enable Selective Ethanol-to-Acetate Conversion.

The fermentation of biomass allows for the generation of major renewable ethanol biofuel that has high energy density favorable for direct alcohol fuel cells in alkaline media. However, selective conversion of ethanol to either CO2 or acetate remains a great challenge. Especially, the ethanol-to-acetate route usually demonstrates decentoxidation current density relative to the ethanol-to-CO2 route that contains strongly adsorbed poisons. This makes the total oxidation of ethanol to CO2 unnecessary. Here, we present a highly active ethanol oxidation electrocatalyst that was prepared by in situ decorating highly dispersed Mo sites on Pd nanosheets (MoOx/Pd) via a surfactant-free and facile route. We found that ∼2 atom % of Mo on Pd nanosheets increases the current density to 3.8 A mgPd-1, around 2 times more active relative to the undecorated Pd nanosheets, achieving nearly 100% faradic efficiency for the ethanol-to-acetate conversion in an alkaline electrolyte without the generation of detectable CO2, evidenced by in situ electrochemical infrared spectroscopy, nuclear magnetic resonance, and ion chromatography. The selective and CO2-free conversion offers a promising strategy through alcohol fuel cells for contributing comparable current density to power electrical equipment while for selective oxidation of biofuels to useful acetate intermediate for the chemical industry.

Nickel Iron Diselenide for Highly Efficient and Selective Electrocatalytic Conversion of Methanol to Formate.

The electro-oxidation of methanol to formate is an interesting example of the potential use of renewable energies to add value to a biosourced chemical commodity. Additionally, methanol electro-oxidation can replace the sluggish oxygen evolution reaction when coupled to hydrogen evolution or to the electroreduction of other biomass-derived intermediates. But the cost-effective realization of these reaction schemes requires the development of efficient and low-cost electrocatalysts. Here, a noble metal-free catalyst, Ni1- x Fex Se2 nanorods, with a high potential for an efficient and selective methanol conversion to formate is demonstrated. At its optimum composition, Ni0.75 Fe0.25 Se2 , this diselenide is able to produce 0.47 mmol cm-2  h-1 of formate at 50 mA cm-2 with a Faradaic conversion efficiency of 99%. Additionally, this noble-metal-free catalyst is able to continuously work for over 50 000 s with a minimal loss of efficiency, delivering initial current densities above 50 mA cm-2 and 2.2 A mg-1 in a 1.0 m KOH electrolyte with 1.0 m methanol at 1.5 V versus reversible hydrogen electrode. This work demonstrates the highly efficient and selective methanol-to-formate conversion on Ni-based noble-metal-free catalysts, and more importantly it shows a very promising example to exploit the electrocatalytic conversion of biomass-derived chemicals.