Surface-Diffusion-Induced Amorphization of Pt Nanoparticles over Ru Oxide Boost Acidic Oxygen Evolution.

Phase transformation offers an alternative strategy for the synthesis of nanomaterials with unconventional phases, allowing us to further explore their unique properties and promising applications. Herein, we first observed the amorphization of Pt nanoparticles on the RuO2 surface by in situ scanning transmission electron microscopy. Density functional theory calculations demonstrate the low energy barrier and thermodynamic driving force for Pt atoms transferring from the Pt cluster to the RuO2 surface to form amorphous Pt. Remarkably, the as-synthesized amorphous Pt/RuO2 exhibits 14.2 times enhanced mass activity compared to commercial RuO2 catalysts for the oxygen evolution reaction (OER). Water electrolyzer with amorphous Pt/RuO2 achieves 1.0 A cm-2 at 1.70 V and remains stable at 200 mA cm-2 for over 80 h. The amorphous Pt layer not only optimized the *O binding but also enhanced the antioxidation ability of amorphous Pt/RuO2, thereby boosting the activity and stability for the OER.

Plasma-Assisted Synthesis of Metal Nitrides for an Efficient Platinum-Group-Metal-Free Anion-Exchange-Membrane Fuel Cell.

In comparison to the well-developed proton-exchange-membrane fuel cells, anion-exchange-membrane fuel cells (AEMFCs) permit adoption of platinum-group-metal (PGM)-free catalysts due to the alkaline environment, giving a substantial cost reduction. However, previous AEMFCs have generally shown unsatisfactory performances due to the lack of effective PGM-free catalysts that can endure harsh fuel cell conditions. Here we report a plasma-assisted synthesis of high-quality nickel nitride (Ni3N) and zirconium nitride (ZrN) employing dinitrogen as the nitrogen resource, exhibiting exceptional catalytic performances toward hydrogen oxidation and oxygen reduction in an alkaline enviroment, respectively. A PGM-free AEMFC assembled by using Ni3N as the anode and ZrN as the cathode delivers power densities of 256 mW cm-2 under an H2-O2 condition and 151 mW cm-2 under an H2-air condition. Furthermore, the fuel cell shows no evidence of degradation after 25 h of operation. This work creates opportunities for developing high-performance and durable AEMFCs based on metal nitrides.

Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO2 Electroreduction.

The electrosynthesis of valuable multicarbon chemicals using carbon dioxide (CO2) as a feedstock has substantially progressed recently but still faces considerable challenges. A major difficulty lines in the sluggish kinetics of forming carbon-carbon (C-C) bonds, especially in neutral media. We report here that oxide-derived copper crystals enclosed by six {100} and eight {111} facets can reduce CO2 to multicarbon products with a high Faradaic efficiency of 74.9 ± 1.7% at a commercially relevant current density of 300 mA cm-2 in 1 M KHCO3 (pH ∼ 8.4). By combining the experimental and computational studies, we uncovered that Cu(100)/Cu(111) interfaces offer a favorable local electronic structure that enhances *CO adsorption and lowers C-C coupling activation energy barriers, performing superior to Cu(100) and Cu(111) surfaces, respectively. On this catalyst, no obvious degradation was observed at 300 mA cm-2 over 50 h of continuous operation.

Unveiling the High Catalytic Activity of a Dinuclear Iron Complex for the Oxygen Evolution Reaction.

The dinuclear iron complex [(H2O)-FeIII-(ppq)-O-(ppq)-FeIII-Cl]3+ (FeIII(ppq), ppq = 2-(pyrid-2'-yl)-8-(1″,10″-phenanthrolin-2″-yl)-quinoline) demonstrates a catalytic activity about one order of magnitude higher than the mononuclear iron complex [Cl-FeIII(dpa)-Cl]+ (FeIII(dpa), dpa = N,N-di(1,10-phenanthrolin-2-yl)-N-isopentylamine) for the oxygen evolution reaction (OER). However, the mechanism behind such an unusually high activity has remained largely unclear. To solve this puzzle, a decomposition-and-reaction mechanism is proposed for the OER with the dinuclear FeIII(ppq) complex as the initial state of the catalytic agent. In this mechanism, the high-valent dinuclear iron complex first dissociates into two mononuclear moieties, and the oxidized mononuclear iron complexes directly catalyze the formation of an O-O bond through a nitrate attack pathway with nitrate functioning as a cocatalyst. Density functional theory calculations reveal that it is the electron-deficient microenvironment around the iron center that gives rise to the remarkable catalytic activity observed experimentally. Therefore, the outstanding performance of the FeIII(ppq) catalyst can be ascribed to the high reactivity of its mononuclear moieties in a high oxidation state, which is concomitant with the structural stability of the low-valent dinuclear complex. The theoretical insights provided by this study could be useful for the optimization and design of novel iron-based water oxidation catalysts.

An Efficient Turing-Type Ag2 Se-CoSe2 Multi-Interfacial Oxygen-Evolving Electrocatalyst*.

Although the Turing structures, or stationary reaction-diffusion patterns, have received increasing attention in biology and chemistry, making such unusual patterns on inorganic solids is fundamentally challenging. We report a simple cation exchange approach to produce Turing-type Ag2 Se on CoSe2 nanobelts relied on diffusion-driven instability. The resultant Turing-type Ag2 Se-CoSe2 material is highly effective to catalyze the oxygen evolution reaction (OER) in alkaline electrolytes with an 84.5 % anodic energy efficiency. Electrochemical measurements show that the intrinsic OER activity correlates linearly with the length of Ag2 Se-CoSe2 interfaces, determining that such Turing-type interfaces are more active sites for OER. Combing X-ray absorption and computational simulations, we ascribe the excellent OER performance to the optimized adsorption energies for critical oxygen-containing intermediates at the unconventional interfaces.

Strongly Coupled Cobalt Diselenide Monolayers for Selective Electrocatalytic Oxygen Reduction to H2 O2 under Acidic Conditions.

Electrosynthesis of hydrogen peroxide (H2 O2 ) in the acidic environment could largely prevent its decomposition to water, but efficient catalysts that constitute entirely earth-abundant elements are lacking. Here we report the experimental demonstration of narrowing the interlayer gap of metallic cobalt diselenide (CoSe2 ), which creates high-performance catalyst to selectively drive two-electron oxygen reduction toward H2 O2 in an acidic electrolyte. The enhancement of the interlayer coupling between CoSe2 atomic layers offers a favorable surface electronic structure that weakens the critical *OOH adsorption, promoting the energetics for H2 O2 production. Consequently, on the strongly coupled CoSe2 catalyst, we achieved Faradaic efficiency of 96.7 %, current density of 50.04 milliamperes per square centimeter, and product rate of 30.60 mg cm-2 h-1 . Moreover, this catalyst shows no sign of degradation when operating at -63 milliamperes per square centimeter over 100 hours.

High-Curvature Transition-Metal Chalcogenide Nanostructures with a Pronounced Proximity Effect Enable Fast and Selective CO2 Electroreduction.

A considerable challenge in the conversion of carbon dioxide into useful fuels comes from the activation of CO2 to CO2 .- or other intermediates, which often requires precious-metal catalysts, high overpotentials, and/or electrolyte additives (e.g., ionic liquids). We report a microwave heating strategy for synthesizing a transition-metal chalcogenide nanostructure that efficiently catalyzes CO2 electroreduction to carbon monoxide (CO). We found that the cadmium sulfide (CdS) nanoneedle arrays exhibit an unprecedented current density of 212 mA cm-2 with 95.5±4.0 % CO Faraday efficiency at -1.2 V versus a reversible hydrogen electrode (RHE; without iR correction). Experimental and computational studies show that the high-curvature CdS nanostructured catalyst has a pronounced proximity effect which gives rise to large electric field enhancement, which can concentrate alkali-metal cations resulting in the enhanced CO2 electroreduction efficiency.

Scaled-Up Synthesis of Amorphous NiFeMo Oxides and Their Rapid Surface Reconstruction for Superior Oxygen Evolution Catalysis.

The anode oxygen evolution reaction (OER) is known to largely limit the efficiency of electrolyzers owing to its sluggish kinetics. While crystalline metal oxides are promising as OER catalysts, their amorphous phases also show high activities. Efforts to produce amorphous metal oxides have progressed slowly, and how an amorphous structure benefits the catalytic performances remains elusive. Now the first scalable synthesis of amorphous NiFeMo oxide (up to 515 g in one batch) is presented with homogeneous elemental distribution via a facile supersaturated co-precipitation method. In contrast to its crystalline counterpart, amorphous NiFeMo oxide undergoes a faster surface self-reconstruction process during OER, forming a metal oxy(hydroxide) active layer with rich oxygen vacancies, leading to superior OER activity (280 mV overpotential at 10 mA cm-2 in 0.1 m KOH). This opens up the potential of fast, facile, and scale-up production of amorphous metal oxides for high-performance OER catalysts.

Theoretical insights into the reactivity of Fe-based catalysts for water oxidation: the role of electron-withdrawing groups.

Recent experiments have shown that complex (1), [Fe(OTf)2(Pytacn)] (OTf = CF3SO3-, Pytacn = 1-(2'-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane), is a promising artificial photosynthetic catalyst because of its distinct capability in water oxidation. Experimentalists have also synthesized several derivatives, e.g., [Fe(OTf)2(E,HPytacn)] (E = -Cl (2), -CO2Et (3) and -NO2 (4)) and [Fe(OTf)2 (E,RPytacn)] (R = -F (5) and R = -Me (6)), and proposed that the E-substituted electron-withdrawing groups could improve the catalytic efficiency. However, the mechanism remains somewhat unclear, especially on the relative catalytic efficiency of these complexes. In this work, we propose an oxygen radical mechanism based on density functional theory (DFT) calculations for the six complexes. The crucial O-O bond-formation step is elucidated. Our calculations reveal that the FeIV-oxyl radical is the active species during the reaction, and the catalytic activities follow the sequence of (4) > (3) > (2) > (1) > (5) > (6), which agrees consistently with the experimental findings. Furthermore, we propose a simple charge-pair interaction model to characterize the effect of electron-withdrawing groups on the catalytic efficiency. It is clearly demonstrated that an electron-withdrawing group with a higher electronegativity is associated with a lower Gibbs free energy barrier for the O-O bond formation, which then leads to a more active catalyst. We also emphasize that the accurate description of dispersive interactions in DFT calculations is crucially important to retrieve the correct sequence of the catalytic efficiency. The theoretical insights provided in this work could be useful for the design of highly efficient Fe-based water oxidation catalysts.

Synthesis of Sub-2†nm Iron-Doped NiSe2 Nanowires and Their Surface-Confined Oxidation for Oxygen Evolution Catalysis.

Ultrathin nanostructures are attractive for diverse applications owing to their unique properties compared to their bulk materials. Transition-metal chalcogenides are promising electrocatalysts, yet it remains difficult to make ultrathin structures (sub-2 nm), and the realization of their chemical doping is even more challenging. Herein we describe a soft-template mediated colloidal synthesis of Fe-doped NiSe2 ultrathin nanowires (UNWs) with diameter down to 1.7 nm. The synergistic interplay between oleylamine and 1-dodecanethiol is crucial to yield these UNWs. The in situ formed amorphous hydroxide layers that is confined to the surface of the ultrathin scaffolds enable efficient oxygen evolution electrocatalysis. The UNWs exhibit a very low overpotential of 268 mV at 10 mA cm-2 in 0.1 m KOH, as well as remarkable long-term stability, representing one of the most efficient noble-metal-free catalysts.

Rational Ligand Design for an Efficient Biomimetic Water Splitting Complex.

Being an important biomimetic model catalyst for water oxidation, the dimanganese molecular complex [H2O(terpy)MnIII(µ-O)2MnIV(terpy)OH2]3+ (complex 1, terpy = 2,2':6',2″-terpyridine) has been investigated extensively by experimentalists. By carrying out density functional theory calculations, we explore theoretically the oxygen evolution mechanisms of complex 1. On the basis of understandings of the geometric and electronic structural features of complex 1, we explore the possibility of improving its catalytic efficiency through a rational design of ligands coordinated to the manganese ions. Recognizing that the rate-determining step of oxygen evolution is the formation of an O-O bond at a high-valent manganese center, we design a new complex, [H2O(2-bpnp)MnIII(µ-O)2MnIV(2-bpnp)OH2]3+ (complex 2, 2-bpnp = 2-([2,2'-bipyridin]-6-yl)-1,8-naphthyridine). It is verified that the proton-accepting 2-bpnp ligand leads to stabilized hydrogen bonding with surrounding water molecules, and hence, the barrier height associated with O-O bond formation is substantially reduced. Moreover, despite its larger size, the 2-bpnp ligand does not cause steric hindrance for the release of molecular oxygen. Consequently, the proposed complex 2 is expected to outperform the existing complex 1 regarding catalytic efficiency. This work highlights the potential usefulness of rational design toward reaching the high efficiency of the oxygen evolution center in photosystem II.

Efficient acidic hydrogen evolution in proton exchange membrane electrolyzers over a sulfur-doped marcasite-type electrocatalyst.

Large-scale deployment of proton exchange membrane (PEM) water electrolyzers has to overcome a cost barrier resulting from the exclusive adoption of platinum group metal (PGM) catalysts. Ideally, carbon-supported platinum used at cathode should be replaced with PGM-free catalysts, but they often undergo insufficient activity and stability subjecting to corrosive acidic conditions. Inspired by marcasite existed under acidic environments in nature, we report a sulfur doping-driven structural transformation from pyrite-type cobalt diselenide to pure marcasite counterpart. The resultant catalyst drives hydrogen evolution reaction with low overpotential of 67 millivolts at 10 milliamperes per square centimeter and exhibits no degradation after 1000 hours of testing in acid. Moreover, a PEM electrolyzer with this catalyst as cathode runs stably over 410 hours at 1 ampere per square centimeter and 60°C. The marked properties arise from sulfur doping that not only triggers formation of acid-resistant marcasite structure but also tailors electronic states (e.g., work function) for improved hydrogen diffusion and electrocatalysis.

A General Strategy to Immobilize Single-Atom Catalysts in Metal-Organic Frameworks for Enhanced Photocatalysis.

Single-atom catalysts (SACs) are witnessing rapid development due to their high activity and selectivity toward diverse reactions. However, it remains a grand challenge in the general synthesis of SACs, particularly featuring an identical chemical microenvironment and on the same support. Herein, a universal synthetic protocol is developed to immobilize SACs in metal-organic frameworks (MOFs). Significantly, by means of SnO2 as a mediator or adaptor, not only different single-atom metal sites, such as Pt, Cu, and Ni, etc., can be installed, but also the MOF supports can be changed (for example, UiO-66-NH2 , PCN-222, and DUT-67) to afford M1 /SnO2 /MOF architecture. Taking UiO-66-NH2 as a representative, the Pt1 /SnO2 /MOF exhibits approximately five times higher activity toward photocatalytic H2 production than the corresponding Pt nanoparticles (≈2.5 nm) stabilized by SnO2 /UiO-66-NH2 . Remarkably, despite featuring identical parameters in the chemical microenvironment and support in M1 /SnO2 /UiO-66-NH2 , the Pt1 catalyst possesses a hydrogen evolution rate of 2167 µmol g-1 h-1 , superior to the Cu1 and Ni1 counterparts, which is attributed to the differentiated hydrogen binding free energies, as supported by density-functional theory (DFT) calculations. This is thought to be the first report on a universal approach toward the stabilization of SACs with identical chemical microenvironment on an identical support.

Black Phosphorous Mediates Surface Charge Redistribution of CoSe2 for Electrochemical H2 O2 Production in Acidic Electrolytes.

Electrochemical generation of hydrogen peroxide (H2 O2 ) by two-electron oxygen reduction offers a green method to mitigate the current dependence on the energy-intensive anthraquinone process, promising its on-site applications. Unfortunately, in alkaline environments, H2 O2 is not stable and undergoes rapid decomposition. Making H2 O2 in acidic electrolytes can prevent its decomposition, but choices of active, stable, and selective electrocatalysts are significantly limited. Here, the selective and efficient two-electron reduction of oxygen toward H2 O2 in acid by a composite catalyst that is composed of black phosphorus (BP) nailed chemically on the metallic cobalt diselenide (CoSe2 ) surface is reported. It is found that this catalyst exhibits a 91% Faradic efficiency for H2 O2 product at an overpotential of 300 mV. Moreover, it can mediate oxygen to H2 O2 with a high production rate of ≈1530 mg L-1 h-1 cm-2 in a flow-cell reactor. Spectroscopic and computational studies together uncover a BP-induced surface charge redistribution in CoSe2 , which leads to a favorable surface electronic structure that weakens the HOO* adsorption, thus enhancing the kinetics toward H2 O2 formation.

Polymorphic cobalt diselenide as extremely stable electrocatalyst in acidic media via a phase-mixing strategy.

Many platinum group metal-free inorganic catalysts have demonstrated high intrinsic activity for diverse important electrode reactions, but their practical use often suffers from undesirable structural degradation and hence poor stability, especially in acidic media. We report here an alkali-heating synthesis to achieve phase-mixed cobalt diselenide material with nearly homogeneous distribution of cubic and orthorhombic phases. Using water electroreduction as a model reaction, we observe that the phase-mixed cobalt diselenide reaches the current density of 10 milliamperes per square centimeter at overpotential of mere 124 millivolts in acidic electrolyte. The catalyst shows no sign of deactivation after more than 400 h of continuous operation and the polarization curve is well retained after 50,000 potential cycles. Experimental and computational investigations uncover a boosted covalency between Co and Se atoms resulting from the phase mixture, which substantially enhances the lattice robustness and thereby the material stability. The findings provide promising design strategy for long-lived catalysts in acid through crystal phase engineering.