Dilute RuCo Alloy Synergizing Single Ru and Co Atoms as Efficient and CO-Resistant Anode Catalyst for Anion Exchange Membrane Fuel Cells.

Ruthenium (Ru) is considered a promising candidate catalyst for alkaline hydroxide oxidation reaction (HOR) due to its hydrogen binding energy (HBE) like that of platinum (Pt) and its much higher oxygenophilicity than that of Pt. However, Ru still suffers from insufficient intrinsic activity and CO resistance, which hinders its widespread use in anion exchange membrane fuel cells (AEMFCs). Here, we report a hybrid catalyst (RuCo)NC+SAs/N-CNT consisting of dilute RuCo alloy nanoparticles and atomically single Ru and Co atoms on N-doped carbon nanotubes The catalyst exhibits a state-of-the-art activity with a high mass activity of 7.35 A mgRu-1. More importantly, when (RuCo)NC+SAs/N-CNT is used as an anode catalyst for AEMFCs, its peak power density reaches 1.98 W cm-2, which is one of the best AEMFCs properties of noble metal-based catalysts at present. Moreover, (RuCo)NC+SAs/N-CNT has superior long-time stability and CO resistance. The experimental and density functional theory (DFT) results demonstrate that the dilute alloying and monodecentralization of the exotic element Co greatly modulates the electronic structure of the host element Ru, thus optimizing the adsorption of H and OH and promoting the oxidation of CO on the catalyst surface, and then stimulates alkaline HOR activity and CO tolerance of the catalyst.

Ru/Ir-Based Electrocatalysts for Oxygen Evolution Reaction in Acidic Conditions: From Mechanisms, Optimizations to Challenges.

The generation of green hydrogen by water splitting is identified as a key strategic energy technology, and proton exchange membrane water electrolysis (PEMWE) is one of the desirable technologies for converting renewable energy sources into hydrogen. However, the harsh anode environment of PEMWE and the oxygen evolution reaction (OER) involving four-electron transfer result in a large overpotential, which limits the overall efficiency of hydrogen production, and thus efficient electrocatalysts are needed to overcome the high overpotential and slow kinetic process. In recent years, noble metal-based electrocatalysts (e.g., Ru/Ir-based metal/oxide electrocatalysts) have received much attention due to their unique catalytic properties, and have already become the dominant electrocatalysts for the acidic OER process and are applied in commercial PEMWE devices. However, these noble metal-based electrocatalysts still face the thorny problem of conflicting performance and cost. In this review, first, noble metal Ru/Ir-based OER electrocatalysts are briefly classified according to their forms of existence, and the OER catalytic mechanisms are outlined. Then, the focus is on summarizing the improvement strategies of Ru/Ir-based OER electrocatalysts with respect to their activity and stability over recent years. Finally, the challenges and development prospects of noble metal-based OER electrocatalysts are discussed.

Engineering Electronic Structure of Nitrogen-Carbon Sites by sp3 -Hybridized Carbon and Incorporating Chlorine to Boost Oxygen Reduction Activity.

Development of efficient and easy-to-prepare low-cost oxygen reaction electrocatalysts is essential for widespread application of rechargeable Zn-air batteries (ZABs). Herein, we mixed NaCl and ZIF-8 by simple physical milling and pyrolysis to obtain a metal-free porous electrocatalyst doped with Cl (mf-pClNC). The mf-pClNC electrocatalyst exhibits a good oxygen reduction reaction (ORR) activity (E1/2 =0.91 V vs. RHE) and high stability in alkaline electrolyte, exceeding most of the reported transition metal carbon-based electrocatalysts and being comparable to commercial Pt/C electrocatalysts. Likewise, the mf-pClNC electrocatalyst also shows state-of-the-art ORR activity and stability in acidic electrolyte. From experimental and theoretical calculations, the better ORR activity is most likely originated from the fact that the introduced Cl promotes the increase of sp3 -hybridized carbon, while the sp3 -hybridized carbon and Cl together modify the electronic structure of the N-adjacent carbons, as the active sites, while NaCl molten-salt etching provides abundant paths for the transport of electrons/protons. Furthermore, the liquid rechargeable ZAB using the mf-pClNC electrocatalyst as the cathode shows a fulfilling performance with a peak power density of 276.88 mW cm-2 . Flexible quasi-solid-state rechargeable ZAB constructed with the mf-pClNC electrocatalyst as the cathode exhibits an exciting performance both at low, high and room temperatures.

Near-Atomic-Scale Superfine Alloy Clusters for Ultrastable Acidic Hydrogen Electrocatalysis.

As a commercial electrode material for proton-exchange membrane water electrolyzers and fuel cells, Pt-based catalysts still face thorny issues, such as insufficient mass activity, stability, and CO tolerance. Here, we construct a bifunctional catalyst consisting of Pt-Er alloy clusters and atomically dispersed Pt and Er single atoms, which exhibits excellent activity, durability, and CO tolerance of acidic hydrogen evolution and oxidation reactions (HER and HOR). The catalyst possesses a remarkably high mass activity and TOF for HER at 63.9 times and 7.2 times more than that of Pt/C, respectively. More impressively, it can operate stably in the acidic electrolyte at 1000 mA cm-2 for more than 1200 h, thereby confirming its potential for practical applications at the industrial current density. In addition, the catalyst also demonstrates a distinguished HOR performance and outstanding CO tolerance. The synergistic effects of active sites give the catalyst exceptional activity for the hydrogen reaction, while the introduction of Er atoms greatly enhances its stability and CO tolerance. This work provides a promising idea for designing low-Pt-loading acidic HER electrocatalysts that are durable at ampere-level current densities and for constructing HOR catalysts with high CO tolerance.

Recent Advances on Single-Atom Catalysts for Photocatalytic CO2 Reduction.

The present energy crisis and environmental challenges may be efficiently resolved by converting carbon dioxide (CO2 ) into various useful carbon products. The development of more effective catalysts has been the main focus of current research on photocatalytic CO2 reduction. Due to their high atomic efficiency and superior catalytic activity, single-atom catalysts (SACs) have attracted considerable interest in catalytic CO2 conversion. This review discusses the current research developments, obstacles, and potential of SACs for photocatalytic CO2 reduction. And further, discusses the principle of photocatalytic carbon dioxide reduction. This work has compared and analyzed the effects of support materials and active site types in SACs on photocatalytic CO2 reduction performance. This work believes that by sharing these developments, some inspiration for the rational design and development of stable and effective photocatalytic CO2 reduction catalysts based on SACs can be provided.

Design and Synthesis of Noble Metal-Based Alloy Electrocatalysts and Their Application in Hydrogen Evolution Reaction.

Hydrogen energy is regarded as the ultimate energy source for future human society, and the preparation of hydrogen from water electrolysis is recognized as the most ideal way. One of the key factors to achieve large-scale hydrogen production by water splitting is the availability of highly active and stable electrocatalysts. Although non-precious metal electrocatalysts have made great strides in recent years, the best hydrogen evolution reaction (HER) electrocatalysts are still based on noble metals. Therefore, it is particularly important to improve the overall activity of the electrocatalysts while reducing the noble metals load. Alloying strategies can shoulder the burden of optimizing electrocatalysts cost and improving electrocatalysts performance. With this in mind, recent work on the application of noble metal-based alloy electrocatalysts in the field of hydrogen production from water electrolysis is summarized. In this review, first, the mechanism of HER is described; then, the current development of synthesis methods for alloy electrocatalysts is presented; finally, an example analysis of practical application studies on alloy electrocatalysts in hydrogen production is presented. In addition, at the end of this review, the prospects, opportunities, and challenges facing noble metal-based alloy electrocatalysts are tried to discuss.

The Factors Dictating Properties of Atomically Precise Metal Nanocluster Electrocatalysts.

Metal nanoparticles occupy an important position in electrocatalysis. Unfortunately, by using conventional synthetic methodology, it is a great challenge to realize the monodisperse composition/structure of metal nanoparticles at the atomic level, and to establish correlations between the catalytic properties and the structure of individual catalyst particles. For the study of well-defined nanocatalysts, great advances have been made for the successful synthesis of nanoparticles with atomic precision, notably ligand-passivated metal nanoclusters. Such well-defined metal nanoclusters have become a type of model catalyst and have shown great potential in catalysis research. In this review, the authors summarize the advances in the utilization of atomically precise metal nanoclusters for electrocatalysis. In particular, the factors (e.g., size, metal doping/alloying, ligand engineering, support materials as well as charge state of clusters) affecting selectivity and activity of catalysts are highlighted. The authors aim to provide insightful guidelines for the rational design of electrocatalysts with high performance and perspectives on potential challenges and opportunities in this emerging field.

Single-Atom Fe Catalysts for Fenton-Like Reactions: Roles of Different N Species.

Recognizing and controlling the structure-activity relationships of single-atom catalysts (SACs) is vital for manipulating their catalytic properties for various practical applications. Herein, Fe SACs supported on nitrogen-doped carbon (SA-Fe/CN) are reported, which show high catalytic reactivity (97% degradation of bisphenol A in only 5 min), high stability (80% of reactivity maintained after five runs), and wide pH suitability (working pH range 3-11) toward Fenton-like reactions. The roles of different N species in these reactions are further explored, both experimentally and theoretically. It is discovered that graphitic N is an adsorptive site for the target molecule, pyrrolic N coordinates with Fe(III) and plays a dominant role in the reaction, and pyridinic N, coordinated with Fe(II), is only a minor contributor to the reactivity of SA-Fe/CN. Density functional theory (DFT) calculations reveal that a lower d-band center location of pyrrolic-type Fe sites leads to the easy generation of Fe-oxo intermediates, and thus, excellent catalytic properties.

Recent Advances in Flexible Zn-Air Batteries: Materials for Electrodes and Electrolytes.

Flexible Zn-air batteries (ZABs) draw much attention due to the merits of high energy density, stability, and safety, and show potential applications for wearable devices. However, the development of flexible ZABs with great energy density, high round-trip efficiency, and long cycle life for practical applications is highly restricted by the lack of highly active oxygen catalysts, high ion-conducting solid-state electrolytes, appropriate Zn anodes, and advanced battery configuration. Promising oxygen catalysts should possess both, superior oxygen reduction reaction and oxygen evolution reaction performance and can be directly used as self-supporting cathodes without loading catalysts on support materials such as carbon cloth. In addition, electrolytes play an important role in ZABs; a good electrolyte should be in all-solid state with high ion conductivity. Moreover, for an excellent Zn anode, it is required to stably contact the electrolyte interface during the bending process. Therefore, in this review, recent advances in ZABs are summarized, including: i) the powder and 3D self-supporting oxygen catalysts, ii) the species of solid-state electrolytes, and iii) the rational design of Zn anodes. Finally, the challenges and opportunities of this promising field are presented.

Recent Advances in Metal-Gas Batteries with Carbon-Based Nonprecious Metal Catalysts.

Metal-gas batteries draw a lot of attention due to their superiorities in high energy density and stable performance. However, the sluggish electrochemical reactions and associated side reactions in metal-gas batteries require suitable catalysts, which possess high catalytic activity and selectivity. Although precious metal catalysts show a higher catalytic activity, high cost of the precious metal catalysts hinders their commercial applications. In contrast, nonprecious metal catalysts complement the weakness of cost, and the gap in activity can be made up by increasing the amount of the nonprecious metal active centers. Herein, recent work on carbon-based nonprecious metal catalysts for metal-gas batteries is summarized. This review starts with introducing the advantages of carbon-based nonprecious metal catalysts, followed by a discussion of the synthetic strategy of carbon-based nonprecious metal catalysts and classification of active sites, and finally a summary of present metal-gas batteries with the carbon-based nonprecious metal catalysts is presented. The challenges and opportunities for carbon-based nonprecious metal catalysts in metal-gas batteries are also explored.

Ultrastable FeCo Bifunctional Electrocatalyst on Se-Doped CNTs for Liquid and Flexible All-Solid-State Rechargeable Zn-Air Batteries.

The rechargeable Zn-air batteries as an environmentally friendly sustainable energy technology have been extensively studied. However, it is still a challenge to develop non-noble metal bifunctional catalysts with high oxygen reduction as well as oxygen evolution reaction (ORR and OER) activity and superior durability, which limit the large-scale application of rechargeable Zn-air batteries. Herein, we synthesized an ultrastable FeCo bifunctional oxygen electrocatalyst on Se-doped CNTs (FeCo/Se-CNT) via a gravity guided chemical vapor deposition (CVD) strategy. The catalyst exhibits excellent ORR (E1/2 = 0.9 V) and OER (overpotential at 10 mA cm-2 = 340 mV) properties simultaneously, surpassing commercial Pt/C and RuO2/C catalysts. More importantly, the catalyst shows an unordinary stability, that is, is no obvious decrease after 30K cycles accelerated durability test for ORR and OER processes. The small potential gap (0.75 V) represents superior bifunctional ORR and OER activities of the FeCo/Se-CNT catalyst. The FeCo/Se-CNT catalyst possesses outstanding electrochemical performance for the rechargeable liquid and flexible all-solid-state Zn-air batteries, for example, a high open circuit voltage (OCV) and peak power density of 1.543 and 1.405 V and 173.4 and 37.5 mW cm-2, respectively.

Single-Atom Co-N4 Electrocatalyst Enabling Four-Electron Oxygen Reduction with Enhanced Hydrogen Peroxide Tolerance for Selective Sensing.

Electrocatalysis of the four-electron oxygen reduction reaction (ORR) provides a promising approach for energy conversion, storage, and oxygen monitoring. However, it is always accompanied by the reduction of hydrogen peroxide (H2O2) on most employed catalysts, which brings down the electrocatalytic selectivity. Here, we report a single-atom Co-N4 electrocatalyst for the four-electron ORR at an onset potential of 0.68 V (vs RHE) in neutral media while with high H2O2 tolerance, outperforming commercial Pt electrocatalysts. Electrochemical kinetic analysis confirms that the Co-N4 catalytic sites dominantly promote the direct four-electron pathway of the ORR rather than the two sequential two-electron reduction pathways with H2O2 as the intermediate. Density functional theory calculations reveal that H2O2 reduction is hampered by the weak adsorption of H2O2 on the porphyrin-like Co centers. This endows the electrocatalyst with improved resistance to current interference from H2O2, enabling highly selective O2 sensing as validated by the reliable sensing performance in vivo. Our study demonstrates the intriguing advantage of single-atom catalysts with high capacity for tailoring metal-adsorbate interactions, broadening their applications in environmental and life monitoring.

Bioinspired Copper Single-Atom Catalysts for Tumor Parallel Catalytic Therapy.

The oxidation of intracellular biomolecules by reactive oxygen species (ROS) forms the basis for ROS-based tumor therapy. However, the current therapeutic modalities cannot catalyze H2 O2 and O2 concurrently for ROS generation, thereby leading to unsatisfactory therapeutic efficacy. Herein, it is reported a bioinspired hollow N-doped carbon sphere doped with a single-atom copper species (Cu-HNCS) that can directly catalyze the decomposition of both oxygen and hydrogen peroxide to ROS, namely superoxide ion (O2 •- ) and the hydroxyl radical (•OH), respectively, in an acidic tumor microenvironment for the oxidation of intracellular biomolecules without external energy input, thus resulting in an enhanced tumor growth inhibitory effect. Notably, the Fenton reaction turnover frequency of Cu species in Cu-HNCS is ≈5000 times higher than that of Fe in commercial Fe3 O4 nanoparticles. Experimental results and density functional theory calculations reveal that the high catalytic activity of Cu-HNCS originates from the single-atom copper, and the calculation predicts a next-generation Fenton catalyst. This work provides an effective paradigm of tumor parallel catalytic therapy for considerably enhanced therapeutic efficacy.

Isolating contiguous Pt atoms and forming Pt-Zn intermetallic nanoparticles to regulate selectivity in 4-nitrophenylacetylene hydrogenation.

Noble metals play a momentous role in heterogeneous catalysis but still face a huge challenge in selectivity control. Herein, we report isolating contiguous Pt atoms and forming Pt-Zn intermetallic nanoparticles as an effective strategy to optimize the selectivity of Pt catalysts. Contiguous Pt atoms are isolated into single atoms and Pt-Zn intermetallic nanoparticles are formed which are supported on hollow nitrogen-doped carbon nanotubes (PtZn/HNCNT), as confirmed by aberration-corrected high-resolution transmission electron microscopy and X-ray absorption spectrometry measurements. Interestingly, this PtZn/HNCNT catalyst promotes the hydrogenation of 4-nitrophenylacetylene to 4-aminophenylacetylene with a much higher conversion ( > 99%) and selectivity (99%) than the comparison samples with Pt isolated-single-atomic-sites (Pt/HNCNT) and Pt nanoparticles (Pt/CN). Further density functional theory (DFT) calculations disclose that the positive Zn atoms assist the adsorption of nitro group and Pt-Zn intermetallic nanoparticles facilitate the hydrogenation on nitro group kinetically.

Heterogeneous Metal-Organic-Framework-Based Biohybrid Catalysts for Cascade Reactions in Organic Solvent.

In cooperative catalysis, the combination of chemo- and biocatalysts to perform one-pot reactions is a powerful tool for the improvement of chemical synthesis. Herein, UiO-66-NH2 was employed to stepwise immobilize Pd nanoparticles (NPs) and Candida antarctica lipase B (CalB) for the fabrication of biohybrid catalysts for cascade reactions. Distinct from traditional materials, UiO-66-NH2 has a robust but tunable structure that can be utilized with a ligand exchange approach to adjust its hydrophobicity, resulting in excellent catalyst dispersity in diverse reaction media. These attractive properties contribute to the formation of MOF-based biohybrid catalysts with high activity and selectivity in the synthesis of benzyl hexanoate from benzaldehyde and ethyl hexanoate. With this proof-of-concept, we reasonably expect that future tailor-made MOFs can combine other catalysts, ranging from chemical to biological catalysts for applications in industry.

A cocoon silk chemistry strategy to ultrathin N-doped carbon nanosheet with metal single-site catalysts.

Development of single-site catalysts supported by ultrathin two-dimensional (2D) porous matrix with ultrahigh surface area is highly desired but also challenging. Here we report a cocoon silk chemistry strategy to synthesize isolated metal single-site catalysts embedded in ultrathin 2D porous N-doped carbon nanosheets (M-ISA/CNS, M = Fe, Co, Ni). X-ray absorption fine structure analysis and spherical aberration correction electron microscopy demonstrate an atomic dispersion of metal atoms on N-doped carbon matrix. In particular, the Co-ISA/CNS exhibit ultrahigh specific surface area (2105 m2 g-1) and high activity for C-H bond activation in the direct catalytic oxidation of benzene to phenol with hydrogen peroxide at room temperature, while the Co species in the form of phthalocyanine and metal nanoparticle show a negligible activity. Density functional theory calculations discover that the generated O = Co = O center intermediates on the single Co sites are responsible for the high activity of benzene oxidation to phenol.

Ordered Porous Nitrogen-Doped Carbon Matrix with Atomically Dispersed Cobalt Sites as an Efficient Catalyst for Dehydrogenation and Transfer Hydrogenation of N-Heterocycles.

Single-atom catalysts (SACs) have been explored widely as potential substitutes for homogeneous catalysts. Isolated cobalt single-atom sites were stabilized on an ordered porous nitrogen-doped carbon matrix (ISAS-Co/OPNC). ISAS-Co/OPNC is a highly efficient catalyst for acceptorless dehydrogenation of N-heterocycles to release H2 . ISAS-Co/OPNC also exhibits excellent catalytic activity for the reverse transfer hydrogenation (or hydrogenation) of N-heterocycles to store H2 , using formic acid or external hydrogen as a hydrogen source. The catalytic performance of ISAS-Co/OPNC in both reactions surpasses previously reported homogeneous and heterogeneous precious-metal catalysts. The reaction mechanisms are systematically investigated using first-principles calculations and it is suggested that the Eley-Rideal mechanism is dominant.

Isolated Fe and Co dual active sites on nitrogen-doped carbon for a highly efficient oxygen reduction reaction.

We successfully prepared Fe and Co isolated single atoms on metal-organic framework derived nitrogen-doped carbon (FeCo-ISAs/CN) by an adsorption-calcination strategy. The obtained FeCo-ISAs/CN exhibited top-level catalytic reactivity for the alkaline oxygen reduction reaction (ORR) with a half-wave potential of 0.920 V, which was 70 mV more positive than that of commercial Pt/C. Moreover, the catalyst was durable and showed negligible activity decay in the alkaline ORR during 5000 voltage cycles.

Correction: Isolated Fe and Co dual active sites on nitrogen-doped carbon for a highly efficient oxygen reduction reaction.

Correction for 'Isolated Fe and Co dual active sites on nitrogen-doped carbon for a highly efficient oxygen reduction reaction' by Diyang Zhang et al., Chem. Commun., 2018, DOI: 10.1039/c8cc00988k.

A Polymer Encapsulation Strategy to Synthesize Porous Nitrogen-Doped Carbon-Nanosphere-Supported Metal Isolated-Single-Atomic-Site Catalysts.

A novel polymer encapsulation strategy to synthesize metal isolated-single-atomic-site (ISAS) catalysts supported by porous nitrogen-doped carbon nanospheres is reported. First, metal precursors are encapsulated in situ by polymers through polymerization; then, metal ISASs are created within the polymer-derived p-CN nanospheres by controlled pyrolysis at high temperature (200-900 °C). Transmission electron microscopy and N2 sorption results reveal this material to exhibit a nanospheric morphology, a high surface area (≈380 m2 g-1 ), and a porous structure (with micropores and mesopores). Characterization by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure confirms the metal to be present as metal ISASs. This methodology is applicable to both noble and nonprecious metals (M-ISAS/p-CN, M = Co, Ni, Cu, Mn, Pd, etc.). In particular, the Co-ISAS/p-CN nanospheres obtained using this method show comparable (E1/2 = 0.838 V) electrochemical oxygen reduction activity to commercial Pt/C with 20 wt% Pt loading (E1/2 = 0.834 V) in alkaline media, superior methanol tolerance, and outstanding stability, even after 5000 cycles.