Alloying Matters for Ordering: Synthesis of Highly Ordered PtCo Intermetallic Catalysts for Fuel Cells.

Porous carbon-supported atomically ordered intermetallic compounds (IMCs) are promising electrocatalysts in boosting oxygen reduction reaction (ORR) for fuel cell applications. However, the formation mechanism of IMC structures under high temperatures is poorly understood, which hampers the synthesis of highly ordered IMC catalysts with promoted ORR performance. Here, we employ high-temperature X-ray diffraction and energy-dispersive spectroscopic elemental mapping techniques to study the formation process of IMCs, by taking PtCo for example, in an industry-relevant impregnation synthesis. We find that high-temperature annealing is crucial in promoting the formation of alloy particles with a stoichiometric Co/Pt ratio, which in turn is the precondition for transforming the disordered alloys to ordered intermetallic structures at a relatively low temperature. Based on the findings, we accordingly synthesize highly ordered L10-type PtCo catalysts with a remarkable ORR performance in fuel cells.

Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis.

Iridium-based electrocatalysts remain the only practical anode catalysts for proton exchange membrane (PEM) water electrolysis, due to their excellent stability under acidic oxygen evolution reaction (OER), but are greatly limited by their high cost and low reserves. Here, we report a nickel-stabilized, ruthenium dioxide (Ni-RuO2) catalyst, a promising alternative to iridium, with high activity and durability in acidic OER for PEM water electrolysis. While pristine RuO2 showed poor acidic OER stability and degraded within a short period of continuous operation, the incorporation of Ni greatly stabilized the RuO2 lattice and extended its durability by more than one order of magnitude. When applied to the anode of a PEM water electrolyser, our Ni-RuO2 catalyst demonstrated >1,000 h stability under a water-splitting current of 200 mA cm-2, suggesting potential for practical applications. Density functional theory studies, coupled with operando differential electrochemical mass spectroscopy analysis, confirmed the adsorbate-evolving mechanism on Ni-RuO2, as well as the critical role of Ni dopants in stabilization of surface Ru and subsurface oxygen for improved OER durability.

Intermetallic PtFe Electrocatalysts for the Oxygen Reduction Reaction: Ordering Degree-Dependent Performance.

Platinum-based atomically ordered alloys (i.e., intermetallic compounds) have distinct advantages over disordered solid solution counterparts in boosting the cathodic oxygen-reduction reaction (ORR) in proton-exchange-membrane fuel cells. Nevertheless, the pivotal role of ordering degree of intermetallic catalysts in promoting ORR performance has been ignored heavily so far, probably owing to the lack of synthetic routes for controlling the ordering degree, especially for preparing highly ordered intermetallic catalysts. Herein, a family of intermetallic PtFe catalysts with similar particle size of 3-4 nm but varied ordering degree in a wide range of 10-70% are prepared. After constructing the PtFe/Pt core/shell structure with around 3 Pt-layer skin, a positive correlation between the ordering degree of the intermetallic catalysts and their ORR activity and durability is identified. Notably, the highly ordered PtFe/Pt catalyst exhibits a high mass activity of 0.92 A mgPt -1 at 0.9 ViR-corrected as cathode catalyst in H2 -O2 fuel cell, with only 24% loss after accelerated durability tests. The ordering degree-dependent performance can be ascribed to the compressive strain effect induced by the intermetallic PtFe core with smaller lattice parameters, and the more thermodynamically stable intermetallic structure compared to disordered alloys.

Ordering Degree-Dependent Activity of Pt3M (M = Fe, Mn) Intermetallic Nanoparticles for Electrocatalytic Methanol Oxidation.

Atomically ordered intermetallic alloys with unique electronic and geometrical structures are highly attractive for heterogeneous catalysis and electrocatalysis. However, the formation of intermetallic phases generally requires high-temperature annealing to overcome the kinetic energy barrier of atom ordering, which unfortunately causes high material heterogeneity and thus makes it challenging to identify the exact contribution of ordered structures to the improved performance. Here, we prepared a family of small-sized intermetallic core/shell Pt3M@Pt (M = Mn or Fe) catalysts with varied ordering degree by a high-temperature sulfur-confined method. We identified a strong correlation between the ordering degree of the intermetallic Pt3M core of the catalysts and their electrocatalytic activity for the methanol oxidation reaction. Density functional theory calculations show that the intermetallic Pt3M core induces a compressive strain on the Pt-skin, which weakens the CO* binding, lowers the free energy change from CO* to COOH*, and therefore promotes electrocatalytic methanol oxidation.

Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells.

Atomically ordered intermetallic nanoparticles are promising for catalytic applications but are difficult to produce because the high-temperature annealing required for atom ordering inevitably accelerates metal sintering that leads to larger crystallites. We prepared platinum intermetallics with an average particle size of <5 nanometers on porous sulfur-doped carbon supports, on which the strong interaction between platinum and sulfur suppresses metal sintering up to 1000°C. We synthesized intermetallic libraries of small nanoparticles consisting of 46 combinations of platinum with 16 other metal elements and used them to study the dependence of electrocatalytic oxygen-reduction reaction activity on alloy composition and platinum skin strain. The intermetallic libraries are highly mass efficient in proton-exchange-membrane fuel cells and could achieve high activities of 1.3 to 1.8 amperes per milligram of platinum at 0.9 volts.

Understanding the Catalytic Sites of Metal-Nitrogen-Carbon Oxygen Reduction Electrocatalysts.

The development of low-cost catalysts containing earth-abundant elements as alternatives to Pt-based catalysts for the oxygen reduction reaction (ORR) is crucial for the large-scale commercial application of proton exchange membrane fuel cells (PEMFCs). Nonprecious metal-nitrogen-carbon (M-N-C) materials represent the most promising candidates to replace Pt-based catalysts for PEMFCs applications. However, the high-temperature pyrolysis process for the preparation of M-N-C catalysts frequently leads to high structural heterogeneity, that is, the coexistence of various metal-containing sites and N-doped carbon structures. Unfortunately, this impedes the identification of the predominant catalytic active structure, and thus, the further development of highly efficient M-N-C catalysts for the ORR. This Minireview, after a brief introduction to the development of M-N-C ORR catalysts, focuses on the commonly accepted views of predominant catalytic active structures in M-N-C catalysts, including atomically dispersed metal-Nx sites, metal nanoparticles encapsulated with nitrogen-doped carbon structures, synergistic action between metal-Nx sites and encapsulated metal nanoparticles, and metal-free nitrogen-doped carbon structures.

Multilayer stabilization for fabricating high-loading single-atom catalysts.

Metal single-atom catalysts (M-SACs) have emerged as an attractive concept for promoting heterogeneous reactions, but the synthesis of high-loading M-SACs remains a challenge. Here, we report a multilayer stabilization strategy for constructing M-SACs in nitrogen-, sulfur- and fluorine-co-doped graphitized carbons (M = Fe, Co, Ru, Ir and Pt). Metal precursors are embedded into perfluorotetradecanoic acid multilayers and are further coated with polypyrrole prior to pyrolysis. Aggregation of the metals is thus efficiently inhibited to achieve M-SACs with a high metal loading (~16 wt%). Fe-SAC serves as an efficient oxygen reduction catalyst with half-wave potentials of 0.91 and 0.82 V (versus reversible hydrogen electrode) in alkaline and acid solutions, respectively. Moreover, as an air electrode in zinc-air batteries, Fe-SAC demonstrates a large peak power density of 247.7 mW cm-2 and superior long-term stability. Our versatile method paves an effective way to develop high-loading M-SACs for various applications.

A Novel Heterostructure Based on RuMo Nanoalloys and N-doped Carbon as an Efficient Electrocatalyst for the Hydrogen Evolution Reaction.

Heterostructures exhibit considerable potential in the field of energy conversion due to their excellent interfacial charge states in tuning the electronic properties of different components to promote catalytic activity. However, the rational preparation of heterostructures with highly active heterosurfaces remains a challenge because of the difficulty in component tuning, morphology control, and active site determination. Herein, a novel heterostructure based on a combination of RuMo nanoalloys and hexagonal N-doped carbon nanosheets is designed and synthesized. In this protocol, metal-containing anions and layered double hydroxides are employed to control the components and morphology of heterostructures, respectively. Accordingly, the as-made RuMo-nanoalloys-embedded hexagonal porous carbon nanosheets are promising for the hydrogen evolution reaction (HER), resulting in an extremely small overpotential (18 mV), an ultralow Tafel slope (25 mV dec-1 ), and a high turnover frequency (3.57 H2 s-1 ) in alkaline media, outperforming current Ru-based electrocatalysts. First-principle calculations based on typical 2D N-doped carbon/RuMo nanoalloys heterostructures demonstrate that introducing N and Mo atoms into C and Ru lattices, respectively, triggers electron accumulation/depletion regions at the heterosurface and consequently reduces the energy barrier for the HER. This work presents a convenient method for rational fabrication of carbon-metal heterostructures for highly efficient electrocatalysis.

Identification of Catalytic Sites for Oxygen Reduction in Metal/Nitrogen-Doped Carbons with Encapsulated Metal Nanoparticles.

The development of metal-N-C materials as efficient non-precious metal (NPM) catalysts for catalysing the oxygen reduction reaction (ORR) as alternatives to platinum is important for the practical use of proton exchange membrane fuel cells (PEMFCs). However, metal-N-C materials have high structural heterogeneity. As a result of their high-temperature synthesis they often consist of metal-Nx sites and graphene-encapsulated metal nanoparticles. Thus it is hard to identify the active structure of metal-N-C catalysts. Herein, we report a low-temperature NH4 Cl-treatment to etch out graphene-encapsulated nanoparticles from metal-N-C catalysts without destruction of co-existing atomically dispersed metal-Nx sites. Catalytic activity is much enhanced by this selective removal of metallic nanoparticles. Accordingly, we can confirm the spectator role of graphene-encapsulated nanoparticles and the pivotal role of metal-Nx sites in the metal-N-C materials for ORR in the acidic medium.

Hierarchically porous carbons as supports for fuel cell electrocatalysts with atomically dispersed Fe-N x moieties.

The development of high-performance non-platinum group metal (non-PGM) catalysts for the oxygen reduction reaction (ORR) is still of significance in promoting the commercialization of proton exchange membrane fuel cells (PEMFCs). In this work, a "hierarchically porous carbon (HPC)-supporting" approach was developed to synthesize highly ORR active Fe-phenanthroline (Fe-phen) derived Fe-N x -C catalysts. Compared to commercial carbon black supports, utilizing HPCs as carbon supports can not only prevent the formation of inactive iron nanoparticles during pyrolysis but also optimize the porous morphology of the catalysts, which eventually increases the amount of reactant-accessible and atomically dispersed Fe-N x active sites. The prepared catalyst therefore exhibits a remarkable ORR activity in both half-cells (half-wave potential of 0.80 V in 0.5 M H2SO4) and H2-air PEMFCs (442 mA cm-2 at a working voltage of 0.6 V), making it among the best non-PGM catalysts for PEMFCs.

A sulfur-tethering synthesis strategy toward high-loading atomically dispersed noble metal catalysts.

Metals often exhibit robust catalytic activity and specific selectivity when downsized into subnanoscale clusters and even atomic dispersion owing to the high atom utilization and unique electronic properties. However, loading of atomically dispersed metal on solid supports with high metal contents for practical catalytic applications remains a synthetic bottleneck. Here, we report the use of mesoporous sulfur-doped carbons as supports to achieve high-loading atomically dispersed noble metal catalysts. The high sulfur content and large surface area endow the supports with high-density anchor sites for fixing metal atoms via the strong chemical metal-sulfur interactions. By the sulfur-tethering strategy, we synthesize atomically dispersed Ru, Rh, Pd, Ir, and Pt catalysts with high metal loading up to 10 wt %. The prepared Pt and Ir catalysts show 30- and 20-fold higher activity than the commercial Pt/C and Ir/C catalysts for catalyzing formic acid oxidation and quinoline hydrogenation, respectively.

Reversing the charge transfer between platinum and sulfur-doped carbon support for electrocatalytic hydrogen evolution.

Metal-support interaction is of great significance for catalysis as it can induce charge transfer between metal and support, tame electronic structure of supported metals, impact adsorption energy of reaction intermediates, and eventually change the catalytic performance. Here, we report the metal size-dependent charge transfer reversal, that is, electrons transfer from platinum single atoms to sulfur-doped carbons and the carbon supports conversely donate electrons to Pt when their size is expanded to ~1.5 nm cluster. The electron-enriched Pt nanoclusters are far more active than electron-deficient Pt single atoms for catalyzing hydrogen evolution reaction, exhibiting only 11 mV overpotential at 10 mA cm-2 and a high mass activity of 26.1 A mg-1 at 20 mV, which is 38 times greater than that of commercial Pt/C. Our work manifests that the manipulation of metal size-dependent charge transfer between metal and support opens new avenues for developing high-active catalysts.

Switching Co/N/C Catalysts for Heterogeneous Catalysis and Electrocatalysis by Controllable Pyrolysis of Cobalt Porphyrin.

Identifying the optimal synthetic and structural parameters in preparing pyrolyzed metal/nitrogen/carbon (M/N/C) materials is crucial for developing effective catalysts for many important catalytic processes. Here we report a group of mesoporous Co/N/C catalysts ranging from polymerized cobalt porphyrin to Co/N-doped carbons, which are prepared by pyrolysis of cobalt porphyrin using silica nanoparticles as templates at different temperatures, for boosting both heterogeneous catalysis and electrocatalysis. It is revealed that the polymerized cobalt porphyrin prepared at low temperature (500°C) is a polymer-like network with exclusive single-atom Co-Nx sites, and that the high-temperature-pyrolysis (>600°C) produces an electrically conductive Co/N-doped carbon, accompanied by part degradation of Co-Nx centers. We identify that the polymerized cobalt porphyrin with undecomposed Co-Nx centers is optimal for heterogeneous catalytic oxidation of ethylbenzene, whereas the electrically conductive Co/N-doped carbon is ideal for eletrocatalytic oxygen reduction. Our results provide new insights for rationally optimizing M/N/C catalysts for different reactions.

[Simulation of algae bloom under different flow velocity].

The construction of a river-type reservoir will normally cause a change of hydrodynamic condition and a decrease of flow velocity in branch bays, leading to the formation of algae bloom when appropriate environmental conditions and sufficient nutrient supply are encountered, and thereby, causing the deterioration of fluvial ecosystem therein. To investigate the effects of hydrodynamic conditions on algae bloom, flow velocity was taken as the characteristic parameter, and controlled differently in the closed and recurrent models under identical environmental and nutrient conditions. The results showed that the increase of the flow velocity in a range of < 0. 4 m x s(-1) would accelerate the growth of algae and the occurrence of bloom. Under the conditions of different flow velocity, the growth of algae was similar to the common process of other microorganisms, namely, lag phase firstly, exponential phase secondly, stationary phase thirdly, and decline phase lastly. Accordingly, the outbreak peak and regression floor of the algae bloom would occur. Therefore, the increase of flow velocity in a range of < 0. 4 m x s(-1) would not inhibit the growth of algae and the occurrence of bloom. The effective characteristic parameter of the hydrodynamic conditions would be studied in depth in future.