Single-Atom Ru Alloyed with Ni Nanoparticles Boosts CO2 Methanation.

Designing catalysts to proceed with catalytic reactions along the desired reaction pathways, e.g., CO2 methanation, has received much attention but remains a huge challenge. This work reports one Ru1Ni single-atom alloy (SAA) catalyst (Ru1Ni/SiO2) prepared via a galvanic replacement reaction between RuCl3 and Ni nanoparticles (NPs) derived from the reduction of Ni phyllosilicate (Ni-ph). Ru1Ni/SiO2 achieved much improved selectivity toward hydrogenation of CO2 to CH4 and catalytic activity (Turnover frequency (TOF) value: 40.00 × 10-3 s-1), much higher than those of Ni/SiO2 (TOF value: 4.40 × 10-3 s-1) and most reported Ni-based catalysts (TOF value: 1.03 × 10-3-11.00 × 10-3 s-1). Experimental studies verify that Ru single atoms are anchored onto the Ni NPs surface via the Ru1-Ni coordination accompanied by electron transfer from Ru1 to Ni. Both in situ experiments and theoretical calculations confirm that the interface sites of Ru1Ni-SAA are the intrinsic active sites, which promote the direct dissociation of CO2 and lower the energy barrier for the hydrogenation of CO* intermediate, thereby directing and enhancing the CO2 hydrogenation to CH4.

Redox Promoted Rapid and Deep Reconstruction of Defect-Rich Nickel Precatalysts for Efficient Water Oxidation.

Understanding the reconstruction mechanism to rationally design cost-effective electrocatalysts for oxygen evolution reaction (OER) is still challenging. Herein, a defect-rich NiMoO4 precatalyst is used to explore its OER activity and reconstruction mechanism. In situ generated oxygen vacancies, distorted lattices, and edge dislocations expedite the deep reconstruction of NiMoO4 to form polycrystalline Ni (oxy)hydroxides for alkaline oxygen evolution. It only needs ≈230 and ≈285 mV to reach 10 and 100 mA cm-2, respectively. The reconstruction boosted by the redox of Ni is confirmed experimentally by sectionalized cyclic voltammetry activations at different specified potential ranges combined with ex situ characterization techniques. Subsequently, the reconstruction route is presented based on the acid-base electronic theory. Accordingly, the dominant contribution of the adsorbate evolution mechanism to reconstruction during oxygen evolution is revealed. This work develops a novel route to synthesize defect-rich materials and provides new tactics to investigate the reconstruction.

Selective Photoelectrochemical Oxidation of Glycerol to Glyceric Acid on (002) Facets Exposed WO3 Nanosheets.

Glycerol is a byproduct of biodiesel production. Selective photoelectrochemical oxidation of glycerol to high value-added chemicals offers an economical and sustainable approach to transform renewable feedstock as well as store green energy at the same time. In this work, we synthesized monoclinic WO3 nanosheets with exposed (002) facets, which could selectively oxidize glycerol to glyceric acid (GLYA) with a photocurrent density of 1.7 mA cm-2 , a 73 % GLYA selectivity and a 39 % GLYA Faradaic efficiency at 0.9 V vs. reversible hydrogen electrode (RHE) under AM 1.5G illumination (100 mW cm-2 ). Compared to (200) facets exposed WO3 , a combination of experiments and theoretical calculations indicates that the superior performance of selective glycerol oxidation mainly originates from the better charge separation and prolonged carrier lifetime resulted from the plenty of surface trapping states, lower energy barrier of the glycerol-to-GLYA reaction pathway, more abundant active sites and stronger oxidative ability of photogenerated holes on the (002) facets exposed WO3 . Our findings show great potential to significantly contribute to the sustainable and environmentally friendly chemical processes via designing high performance photoelectrochemical cell via facet engineering for renewable feedstock transformation.

Amorphous versus Crystalline in Water Oxidation Catalysis: A Case Study of NiFe Alloy.

Catalytic water splitting driven by renewable electricity offers a promising strategy to produce molecular hydrogen, but its efficiency is severely restricted by the sluggish kinetics of the anodic water oxidation reaction. Amorphous catalysts are reported to show better activities of water oxidation than their crystalline counterparts, but little is known about the underlying origin, which retards the development of high-performance amorphous oxygen evolution reaction catalysts. Herein, on the basis of cyclic voltammetry, electrochemical impedance spectroscopy, isotope labeling, and in situ X-ray absorption spectroscopy studies, we demonstrate that an amorphous catalyst can be electrochemically activated to expose active sites in the bulk thanks to the short-range order of the amorphous structure, which greatly increases the number of active sites and thus improves the electrocatalytic activity of the amorphous catalyst in water oxidation.

Elucidating the Electrocatalytic CO2 Reduction Reaction over a Model Single-Atom Nickel Catalyst.

Designing effective electrocatalysts for the carbon dioxide reduction reaction (CO2 RR) is an appealing approach to tackling the challenges posed by rising CO2 levels and realizing a closed carbon cycle. However, fundamental understanding of the complicated CO2 RR mechanism in CO2 electrocatalysis is still lacking because model systems are limited. We have designed a model nickel single-atom catalyst (Ni SAC) with a uniform structure and well-defined Ni-N4 moiety on a conductive carbon support with which to explore the electrochemical CO2 RR. Operando X-ray absorption near-edge structure spectroscopy, Raman spectroscopy, and near-ambient X-ray photoelectron spectroscopy, revealed that Ni+ in the Ni SAC was highly active for CO2 activation, and functioned as an authentic catalytically active site for the CO2 RR. Furthermore, through combination with a kinetics study, the rate-determining step of the CO2 RR was determined to be *CO2 - +H+ →*COOH. This study tackles the four challenges faced by the CO2 RR; namely, activity, selectivity, stability, and dynamics.

Breaking Long-Range Order in Iridium Oxide by Alkali Ion for Efficient Water Oxidation.

Oxygen electrochemistry plays a critical role in clean energy technologies such as fuel cells and electrolyzers, but the oxygen evolution reaction (OER) severely restricts the efficiency of these devices due to its slow kinetics. Here, we show that via incorporation of lithium ion into iridium oxide, the thus obtained amorphous iridium oxide (Li-IrO x) demonstrates outstanding water oxidation activity with an OER current density of 10 mA/cm2 at 270 mV overpotential for 10 h of continuous operation in acidic electrolyte. DFT calculations show that lithium incorporation into iridium oxide is able to lower the activation barrier for OER. X-ray absorption characterizations indicate that both amorphous Li-IrO x and rutile IrO2 own similar [IrO6] octahedron units but have different [IrO6] octahedron connection modes. Oxidation of iridium to higher oxidation states along with shrinkage in the Ir-O bond was observed by in situ X-ray absorption spectroscopy on amorphous Li-IrO x, but not on rutile IrO2 under OER operando conditions. The much more "flexible" disordered [IrO6] octahedrons with higher oxidation states in amorphous Li-IrO x as compared to the periodically interconnected "rigid" [IrO6] octahedrons in crystalline IrO2 are able to act as more electrophilic centers and thus effectively promote the fast turnover of water oxidation.

Single Cobalt Atoms Anchored on Porous N-Doped Graphene with Dual Reaction Sites for Efficient Fenton-like Catalysis.

The Fenton-like process presents one of the most promising strategies to generate reactive oxygen-containing radicals to deal with the ever-growing environmental pollution. However, developing improved catalysts with adequate activity and stability is still a long-term goal for practical application. Herein, we demonstrate single cobalt atoms anchored on porous N-doped graphene with dual reaction sites as highly reactive and stable Fenton-like catalysts for efficient catalytic oxidation of recalcitrant organics via activation of peroxymonosulfate (PMS). Our experiments and density functional theory (DFT) calculations show that the CoN4 site with a single Co atom serves as the active site with optimal binding energy for PMS activation, while the adjacent pyrrolic N site adsorbs organic molecules. The dual reaction sites greatly reduce the migration distance of the active singlet oxygen produced from PMS activation and thus improve the Fenton-like catalytic performance.

Identification of Surface Reactivity Descriptor for Transition Metal Oxides in Oxygen Evolution Reaction.

A number of important reactions such as the oxygen evolution reaction (OER) are catalyzed by transition metal oxides (TMOs), the surface reactivity of which is rather elusive. Therefore, rationally tailoring adsorption energy of intermediates on TMOs to achieve desirable catalytic performance still remains a great challenge. Here we show the identification of a general and tunable surface structure, coordinatively unsaturated metal cation (MCUS), as a good surface reactivity descriptor for TMOs in OER. Surface reactivity of a given TMO increases monotonically with the density of MCUS, and thus the increase in MCUS improves the catalytic activity for weak-binding TMOs but impairs that for strong-binding ones. The electronic origin of the surface reactivity can be well explained by a new model proposed in this work, wherein the energy of the highest-occupied d-states relative to the Fermi level determines the intermediates' bonding strength by affecting the filling of the antibonding states. Our model for the first time well describes the reactivity trends among TMOs, and would initiate viable design principles for, but not limited to, OER catalysts.

Engineering high-valence metal-enriched cobalt oxyhydroxide catalysts for an enhanced OER under near-neutral pH conditions.

Understanding water splitting in pH-neutral media has important implications for hydrogen production from seawater. Despite their significance, electrochemical water oxidation and reduction in neutral electrolytes still face great challenges. This study focuses on designing efficient electrocatalysts capable of promoting the oxygen evolution reaction (OER) in neutral media by incorporating high-valence elements into transition-metal hydroxides. The as-prepared and optimized two-dimensional Mo-Co(OH)2 nanosheets, which undergo operando transformation into oxyhydroxide active species, demonstrated an overpotential of 550 mV at 10 mA cm-2 with a Tafel slope of 110.1 mV dec-1 in 0.5 M KHCO3. In situ X-ray absorption spectroscopy revealed that the incorporation of high-valence elements facilitates the generation of CoOOH active sites at low potential and enhances electron transfer kinetics by altering the electronic environment of the Co center. This study offers new insights for developing more efficient OER electrocatalysts and provides fresh ideas for seawater utilization through the study of the reaction mechanism of the near-neutral-pH OER.

Revisiting the Activity Gap of Iridium Electrocatalysts for Acidic Water Oxidation.

Iridium electrocatalysts have been extensively studied for the acidic water oxidation reaction (2H2O → O2 + 4H+ + 4e-, also known as the oxygen evolution reaction, OER) in recent years. However, the activity of different iridium catalysts, such as amorphous, crystalline, and metallic ones, varies significantly, and there is no common explanation for the origin of this difference. Here four types of iridium catalysts were selected as models and characterized by various techniques. The redox behavior of iridium catalysts and oxidation of hydrogen peroxide (in the form of OOH-) were applied to in situ probe the adsorption energy of oxygen reaction intermediates (*OH, *O, and *OOH) on iridium catalysts under the OER conditions. Structure-activity analysis suggested that the more optimal and broader distribution of adsorption energies on metallic iridium (iridium black) and its good conductivity are the origin of its highest activity among the four different iridium catalysts.

Insight into Key Parameters for Fabricating Stable Single-Atom Pt-Nix Alloy by Reduction Environment-Induced Anti-Ostwald Effects.

Developing single-atom catalysts with superior stability under reduction conditions is essential for hydrogenation/dehydrogenation catalysis and green hydrogen generation. In this contribution, single-atom Pt catalysts were achieved via a reduction environment-induced anti-Ostwald approach in the highly confined Ni species (Pt-Nix ) on nonreducible Al2 O3 matrix. In-situ X-ray absorption spectroscopy indicated that the isolated Pt-Nix metallic bonds, generated at high reduction temperature, dominated the formation of single Pt atoms. A relatively large cluster of metallic Ni would benefit the stabilization of Pt single atom as observed via high-angle annular dark-field scanning transmission electron microscopy and validated by density functional theory simulation. Excellent performance on cellulose hydrogenolysis was demonstrated under harsh reductive and hydrothermal conditions, potentially expandable to other hydrogen involved reactions like CO2 hydrogenation, green hydrogen production from different hydrogen carriers, and beyond.

Progress of Heterogeneous Iridium-Based Water Oxidation Catalysts.

The water oxidation reaction (or oxygen evolution reaction, OER) plays a critical role in green hydrogen production via water splitting, electrochemical CO2 reduction, and nitrogen fixation. The four-electron and four-proton transfer OER process involves multiple reaction intermediates and elementary steps that lead to sluggish kinetics; therefore, a high overpotential is necessary to drive the reaction. Among the different water-splitting electrolyzers, the proton exchange membrane type electrolyzer has greater advantages, but its anode catalysts are limited to iridium-based materials. The iridium catalyst has been extensively studied in recent years due to its balanced activity and stability for acidic OER, and many exciting signs of progress have been made. In this review, the surface and bulk Pourbaix diagrams of iridium species in an aqueous solution are introduced. The iridium-based catalysts, including metallic or oxides, amorphous or crystalline, single crystals, atomically dispersed or nanostructured, and iridium compounds for OER, are then elaborated. The latest progress of active sites, reaction intermediates, reaction kinetics, and elementary steps is summarized. Finally, future research directions regarding iridium catalysts for acidic OER are discussed.

Progress of Nonprecious-Metal-Based Electrocatalysts for Oxygen Evolution in Acidic Media.

Water oxidation, or the oxygen evolution reaction (OER), which combines two oxygen atoms from two water molecules and releases one oxygen molecule, plays the key role by providing protons and electrons needed for the hydrogen generation, electrochemical carbon dioxide reduction, and nitrogen fixation. The multielectron transfer OER process involves multiple reaction intermediates, and a high overpotential is needed to overcome the sluggish kinetics. Among the different water splitting devices, proton exchange membrane (PEM) water electrolyzer offers greater advantages. However, current anode OER electrocatalysts in PEM electrolyzers are limited to precious iridium and ruthenium oxides. Developing highly active, stable, and precious-metal-free electrocatalysts for water oxidation in acidic media is attractive for the large-scale application of PEM electrolyzers. In recent years, various types of precious-metal-free catalysts such as carbon-based materials, earth-abundant transition metal oxides, and multiple metal oxide mixtures have been investigated and some of them show promising activity and stability for acidic OER. In this review, the thermodynamics of water oxidation, Pourbaix diagram of metal elements in aqueous solution, and theoretical screening and prediction of precious-metal-free electrocatalysts for acidic OER are first elaborated. The catalytic performance, reaction kinetics, and mechanisms together with future research directions regarding acidic OER are summarized and discussed.

Structural Evolution and Underlying Mechanism of Single-Atom Centers on Mo2C(100) Support during Oxygen Reduction Reaction.

The single-metal atoms coordinating with the surface atoms of the support constitute the active centers of as-prepared single-atom catalysts (SACs). However, under hash electrochemical conditions, (1) supports' surfaces may experience structural change, which turn to be distinct from those at ambient conditions; (2) during catalysis, the dynamic responses of a single atom to the attack of reaction intermediates likely change the coordination environment of a single atom. These factors could alter the performance of SACs. Herein, we investigate these issues using Mo2C(100)-supported single transition-metal (TM) atoms as model SACs toward catalyzing the oxygen reduction reaction (ORR). It is found that the Mo2C(100) surface is oxidized under ORR turnover conditions, resulting in significantly weakened bonding between single TM atoms and the Mo2C(100) surface (TM@Mo2C(100)_O* term for SAC). While the intermediate in 2 e- ORR does not change the local structures of the active centers in these SACs, the O* intermediate emerging in 4 e- ORR can damage Rh@ and Cu@Mo2C(100)_O*. Furthermore, on the basis of these findings, we propose Pt@Mo2C(100)_O* as a qualified ORR catalyst, which exhibits extraordinary 4 e- ORR activity with an overpotential of only 0.33 V, surpassing the state-of-the-art Pt(111), and thus being identified as a promising alternative to the commercial Pt/C catalyst.

Orbital coupling of hetero-diatomic nickel-iron site for bifunctional electrocatalysis of CO2 reduction and oxygen evolution.

While inheriting the exceptional merits of single atom catalysts, diatomic site catalysts (DASCs) utilize two adjacent atomic metal species for their complementary functionalities and synergistic actions. Herein, a DASC consisting of nickel-iron hetero-diatomic pairs anchored on nitrogen-doped graphene is synthesized. It exhibits extraordinary electrocatalytic activities and stability for both CO2 reduction reaction (CO2RR) and oxygen evolution reaction (OER). Furthermore, the rechargeable Zn-CO2 battery equipped with such bifunctional catalyst shows high Faradaic efficiency and outstanding rechargeability. The in-depth experimental and theoretical analyses reveal the orbital coupling between the catalytic iron center and the adjacent nickel atom, which leads to alteration in orbital energy level, unique electronic states, higher oxidation state of iron, and weakened binding strength to the reaction intermediates, thus boosted CO2RR and OER performance. This work provides critical insights to rational design, working mechanism, and application of hetero-DASCs.

Rational Design of an Iridium-Tungsten Composite with an Iridium-Rich Surface for Acidic Water Oxidation.

Developing highly active and stable water oxidation catalysts with reduced cost in acidic media plays a critical role in clean energy technologies such as fuel cells and electrolyzers. Precious iridium-based oxides are still the only oxygen evolution reaction (OER) catalysts with reasonable activity and stability in acid. Herein, we design iridium-tungsten composites with a metallic tungsten-rich core and an iridium-rich surface by the sol-gel method followed by hydrogen reduction. The thus obtained iridium-tungsten catalyst shows much higher intrinsic water oxidation activity (100 mA/mgIr at an overpotential of 290 mV) and stability (100 h at 10 mA/cm2geom) together with reduced iridium content (33 wt % only) as compared with pure iridium oxide. An operando method using H2O2 as a probe molecule is developed to determine the relative adsorption strength of the reaction intermediates (*OH and *OOH) in the OER process. Detailed characterization shows that the tungsten-incorporated surface not only modulates the adsorption energy of oxygen intermediates on iridium but also enhances the stability of iridium species in acid, while the metallic tungsten core exhibits high electrical conductivity, all of which collectively give rise to the much enhanced catalytic performance of iridium-tungsten composite in acidic water oxidation. A single-membrane electrode assembly is further prepared to demonstrate the advantages and potential application of iridium-tungsten composite in practical proton exchange membrane electrolyzers.

Microenvironment modulation of single-atom catalysts and their roles in electrochemical energy conversion.

Single-atom catalysts (SACs) have become the most attractive frontier research field in heterogeneous catalysis. Since the atomically dispersed metal atoms are commonly stabilized by ionic/covalent interactions with neighboring atoms, the geometric and electronic structures of SACs depend greatly on their microenvironment, which, in turn, determine the performances in catalytic processes. In this review, we will focus on the recently developed strategies of SAC synthesis, with attention on the microenvironment modulation of single-atom active sites of SACs. Furthermore, experimental and computational advances in understanding such microenvironment in association to the catalytic activity and mechanisms are summarized and exemplified in the electrochemical applications, including the water electrolysis and O2/CO2/N2 reduction reactions. Last, by highlighting the prospects and challenges for microenvironment engineering of SACs, we wish to shed some light on the further development of SACs for electrochemical energy conversion.

Coordination engineering of iridium nanocluster bifunctional electrocatalyst for highly efficient and pH-universal overall water splitting.

Water electrolysis offers a promising energy conversion and storage technology for mitigating the global energy and environmental crisis, but there still lack highly efficient and pH-universal electrocatalysts to boost the sluggish kinetics for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER). Herein, we report uniformly dispersed iridium nanoclusters embedded on nitrogen and sulfur co-doped graphene as an efficient and robust electrocatalyst for both HER and OER at all pH conditions, reaching a current density of 10 mA cm-2 with only 300, 190 and 220 mV overpotential for overall water splitting in neutral, acidic and alkaline electrolyte, respectively. Based on probing experiments, operando X-ray absorption spectroscopy and theoretical calculations, we attribute the high catalytic activities to the optimum bindings to hydrogen (for HER) and oxygenated intermediate species (for OER) derived from the tunable and favorable electronic state of the iridium sites coordinated with both nitrogen and sulfur.

Layered Structure Causes Bulk NiFe Layered Double Hydroxide Unstable in Alkaline Oxygen Evolution Reaction.

NiFe-based layered double hydroxides (LDHs) are among the most efficient oxygen evolution reaction (OER) catalysts in alkaline medium, but their long-term OER stabilities are questionable. In this work, it is demonstrated that the layered structure makes bulk NiFe LDH intrinsically not stable in OER and the deactivation mechanism of NiFe LDH in OER is further revealed. Both operando electrochemical and structural characterizations show that the interlayer basal plane in bulk NiFe LDH contributes to the OER activity, and the slow diffusion of proton acceptors (e.g., OH- ) within the NiFe LDH interlayers during OER causes dissolution of NiFe LDH and therefore decrease in OER activity with time. To improve diffusion of proton acceptors, it is proposed to delaminate NiFe LDH into atomically thin nanosheets, which is able to effectively improve OER stability of NiFe LDH especially at industrial operating conditions such as elevated operating temperatures (e.g., at 80 °C) and large current densities (e.g., at 500 mA cm-2 ).

Expedient synthesis of E-hydrazone esters and 1H-indazole scaffolds through heterogeneous single-atom platinum catalysis.

Unprotected E-hydrazone esters are prized building blocks for the preparation of 1H-indazoles and countless other N-containing biologically active molecules. Despite previous advances, efficient and stereoselective synthesis of these compounds remains nontrivial. Here, we show that Pt single atoms anchored on defect-rich CeO2 nanorods (Pt1/CeO2), in conjunction with the alcoholysis of ammonia borane, promotes exceptionally E-selective hydrogenation of α-diazoesters to afford a wide assortment of N-H hydrazone esters with an overall turnover frequency of up to 566 hours-1 upon reaction completion. The α-diazoester substrates could be generated in situ from readily available carboxylic esters in one-pot hydrogenation reaction. Utility is demonstrated through concise, scalable synthesis of 1H-indazole-derived pharmaceuticals and their 15N-labeled analogs. The present protocol highlights a key mechanistic nuance wherein simultaneous coordination of a Pt site with the diazo N═N and ester carbonyl motifs plays a central role in controlling stereoselectivity, which is supported by density functional theory calculations.