VOx Matrix Confinement Approach to Generate Sub-3 nm L10-Pt-Based Intermetallic Catalysts for Fuel Cell Cathode.

Pt-based intermetallic compounds (IMCs) are considered as a class of promising fuel cell electrocatalysts, owing to their outstanding intrinsic activity and durability. However, the synthesis of uniformly dispersed IMCs with small sizes presents a formidable challenge during the essential high-temperature annealing process. Herein, a facile and generally applicable VOx matrix confinement strategy is demonstrated for the controllable synthesis of ordered L10-PtM (M = Fe, Co, and Mn) nanoparticles, which not only enhances the dispersion of intermetallic nanocrystals, even at high loading (40 wt%), but also simplifies the oxide removal and acid-washing procedures. Taking intermetallic PtCo as an example, the as-prepared catalyst displays a high-performance oxygen reduction activity (mass activity of 1.52 A mgPt -1) and excellent stability in the membrane electrode assemblies (MEAs) (the ECSA has just 7% decay after durability test). This strategy provides an economical and scalable route for the controlled synthesis of Pt-based intermetallic catalysts, which can pave a way for the commercialization of fuel cell technologies.

Coronavirus-like Core-Shell-Structured Co@C for Hydrogen Evolution via Hydrolysis of Sodium Borohydride.

Constructing a reliable and robust cobalt-based catalyst for hydrogen evolution via hydrolysis of sodium borohydride is appealing but challenging due to the deactivation caused by the metal leaching and re-oxidization of metallic cobalt. A unique core-shell-structured coronavirus-like Co@C microsphere was prepared via pyrolysis of Co-MOF. This special Co@C had a microporous carbon coating to retain the reduced state of cobalt and resist the metal leaching. Furthermore, several nano-bumps grown discretely on the surface afforded enriched active centers. Applied in the pyrolysis of NaBH4, the Co@C-650, carbonized at 650 °C, exhibited the best activity and reliable recyclability. This comparable performance is ascribed to the increased metallic active sites and robust stability.

Autothermal Reforming of Volatile Organic Compounds to Hydrogen-Rich Gas.

Industrial emissions of volatile organic compounds are urgently addressed for their toxicity and carcinogenicity to humans. Developing efficient and eco-friendly reforming technology of volatile organic compounds is important but still a great challenge. A promising strategy is to generate hydrogen-rich gas for solid oxide fuel cells by autothermal reforming of VOCs. In this study, we found a more desirable commercial catalyst (NiO/K2O-γ-Al2O3) for the autothermal reforming of VOCs. The performance of autothermal reforming of toluene as a model compound over a NiO/K2O-γ-Al2O3 catalyst fitted well with the simulation results at the optimum operating conditions calculated based on a simulation using Aspen PlusV11.0 software. Furthermore, the axial temperature distribution of the catalyst bed was monitored during the reaction, which demonstrated that the reaction system was self-sustaining. Eventually, actual volatile organic compounds from the chemical factory (C9, C10, toluene, paraxylene, diesel, benzene, kerosene, raffinate oil) were completely reformed over NiO/K2O-γ-Al2O3. Reducing emissions of VOCs and generating hydrogen-rich gas as a fuel from the autothermal reforming of VOCs is a promising strategy.

Work Efficiency and Economic Efficiency of Actual Driving Test of Proton Exchange Membrane Fuel Cell Forklift.

A 3.5 tonne forklift containing proton exchange membrane fuel cells (PEMFCs) and lithium-ion batteries was manufactured and tested in a real factory. The work efficiency and economic applicability of the PEMFC forklift were compared with that of a lithium-ion battery-powered forklift. The results showed that the back-pressure of air was closely related to the power density of the stack, whose stability could be improved by a reasonable control strategy and membrane electrode assemblies (MEAs) with high consistency. The PEMFC powered forklift displayed 40.6% higher work efficiency than the lithium-ion battery-powered forklift. Its lower use-cost compared to internal engine-powered forklifts, is beneficial to the commercialization of this product.

Boosting Oxygen Reduction via Integrated Construction and Synergistic Catalysis of Porous Platinum Alloy and Defective Graphitic Carbon.

Integrated fabrication through the strong interaction between catalyst and carrier is crucial to realize efficient oxygen electrocatalysis for fuel cells. We report herein a porous Pt-rich alloy encapsulated by graphitic carbon via integration engineering, where a synergistic catalysis between ternary PtCuCo alloy and graphitic Co-N-C results in the optimized reaction pathway and improved oxygen reduction reaction (ORR) performance. The hybrid catalyst PtCuCo@Co-N-C delivers a mass activity of 1.14 A mgPt -1 at 0.9 V vs. RHE and a peak power density of 960 mW cm-2 in the full-cell assessment, outperforming commercial Pt/C catalyst (0.12 A mgPt -1 and 780 mW cm-2 ). Experimental results combined with theoretical simulations suggest that the mutual assistance between porous Pt alloy and Co-N-C accounts for the enhanced catalytic performance. Such integrated engineering concept is significant for strengthening the anti-corrosion capabilities and improving the ORR performance of Pt-based catalysts.

"One-for-All" Strategy in Fast Energy Storage: Production of Pillared MOF Nanorod-Templated Positive/Negative Electrodes for the Application of High-Performance Hybrid Supercapacitor.

Currently, metal-organic frameworks (MOFs) are intensively studied as active materials for electrochemical energy storage applications due to their tunable structure and exceptional porosities. Among them, water stable pillared MOFs with dual ligands have been reported to exhibit high supercapacitor (SC) performance. Herein, the "One-for-All" strategy is applied to synthesize both positive and negative electrodes of a hybrid SC (HSC) from a single pillared MOF. Specifically, Ni-DMOF-TM ([Ni(TMBDC)(DABCO)0.5 ], TMBDC: 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid, DABCO: 1,4-diazabicyclo[2.2.2]-octane) nanorods are directly grown on carbon fiber paper (CFP) (denoted as CFP@TM-nanorods) with the help of triethylamine and function as the positive electrode of HSC under alkaline electrolyte. Meanwhile, calcinated N-doped hierarchical porous carbon nanorods (CFP@TM-NPCs) are produced and utilized as the negative counter-electrode from a one-step heat treatment of CFP@TM-nanorods. After assembling these two electrodes together to make a hybrid device, the TM-nanorods//TM-NPCs exhibit a wide voltage window of 1.5 V with a high sloping discharge plateau between 1-1.2 V, indicating its great potential for practical applications. This as-described "One-for-All" strategy is widely applicable and highly reproducible in producing MOF-based electrode materials for HSC applications, which shortens the gap between experimental synthesis and practical application of MOFs in fast energy storage.

High-Performance Energy Storage and Conversion Materials Derived from a Single Metal-Organic Framework/Graphene Aerogel Composite.

Metal oxides and carbon-based materials are the most promising electrode materials for a wide range of low-cost and highly efficient energy storage and conversion devices. Creating unique nanostructures of metal oxides and carbon materials is imperative to the development of a new generation of electrodes with high energy and power density. Here we report our findings in the development of a novel graphene aerogel assisted method for preparation of metal oxide nanoparticles (NPs) derived from bulk MOFs (Co-based MOF, Co(mIM)2 (mIM = 2-methylimidazole). The presence of cobalt oxide (CoOx) hollow NPs with a uniform size of 35 nm monodispersed in N-doped graphene aerogels (NG-A) was confirmed by microscopic analyses. The evolved structure (denoted as CoOx/NG-A) served as a robust Pt-free electrocatalyst with excellent activity for the oxygen reduction reaction (ORR) in an alkaline electrolyte solution. In addition, when Co was removed, the resulting nitrogen-rich porous carbon-graphene composite electrode (denoted as C/NG-A) displayed exceptional capacitance and rate capability in a supercapacitor. Further, this method is readily applicable to creation of functional metal oxide hollow nanoparticles on the surface of other carbon materials such as graphene and carbon nanotubes, providing a good opportunity to tune their physical or chemical activities.

Integrating hydrogen utilization in CO2 electrolysis with reduced energy loss.

Electrochemical carbon dioxide reduction reaction using sustainable energy is a promising approach of synthesizing chemicals and fuels, yet is highly energy intensive. The oxygen evolution reaction is particularly problematic, which is kinetically sluggish and causes anodic carbon loss. In this context, we couple CO2 electrolysis with hydrogen oxidation reaction in a single electrochemical cell. A Ni(OH)2/NiOOH mediator is used to fully suppress the anodic carbon loss and hydrogen oxidation catalyst poisoning by migrated reaction products. This cell is highly flexible in producing either gaseous (CO) or soluble (formate) products with high selectivity (up to 95.3%) and stability (>100 h) at voltages below 0.9 V (50 mA cm-2). Importantly, thanks to the "transferred" oxygen evolution reaction to a water electrolyzer with thermodynamically and kinetically favored reaction conditions, the total polarization loss and energy consumption of our H2-integrated CO2 reduction reaction, including those for hydrogen generation, are reduced up to 22% and 42%, respectively. This work demonstrates the opportunity of combining CO2 electrolysis with the hydrogen economy, paving the way to the possible integration of various emerging energy conversion and storage approaches for improved energy/cost effectiveness.

Boosting the activity and stability via synergistic catalysis of Co nanoparticles and MoC to construct a bifunctional electrocatalyst for high-performance and long-life rechargeable zinc-air batteries.

The high overpotential of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) leading to slow air cathode kinetics is still a major challenge for zinc-air batteries (ZABs), hindering the commercialization of ZABs. With the advantages of cost-effectiveness and feasibility of synthesis at room temperature, zeolite imidazole frameworks (ZIFs) are regarded as advanced precursors. But a majority of ZIF-derived catalysts show only one catalytic activity, which limits their performance in ZABs as well as the cycling stability. In addition, molybdenum carbide (MoC) is recognized as an excellent candidate for renewable energy conversion due to its good chemical resistance and thermal stability. Herein, we report a ZIF-67-derived Co/MoC-NC multiphase doped carbon bifunctional ORR/OER catalyst with multiple active sites for the cathode of ZABs. The synergistic catalysis of Co nanoparticles and MoC nanoparticles in Co/MoC-NC which are embedded in a thin layer of N-doped graphitic carbon and immobilized on N-doped graphitic carbon, respectively, demonstrates superior ORR catalytic performance and durability both under alkaline and acidic conditions (E1/2 = 0.87 V in 1.0 M KOH and E1/2 = 0.76 V in 0.5 M H2SO4). Simultaneously, Co/MoC-NC also exhibits favorable OER performance (10 mA cm-2, η = 320 mV) in 1 M KOH. Furthermore, a remarkable peak-power density of 215.36 mW cm-2 and great cycling stability could be achieved while applying Co/MoC-NC in the cathode of ZABs (over 300 h). This work will provide a viable design concept for designing and synthesizing multifunctional catalysts to construct rechargeable ZABs.

An integrated platinum-nanocarbon electrocatalyst for efficient oxygen reduction.

Efficient and robust platinum-carbon electrocatalysts are of great significance for the long-term service of high-performance fuel cells. Here, we report a Pt alloy integrated in a cobalt-nitrogen-nanocarbon matrix by a multiscale design principle for efficient oxygen reduction reaction. This Pt integrated catalyst demonstrates an increased mass activity, 11.7 times higher than that of commercial Pt catalyst, and retains a stability of 98.7% after 30,000 potential cycles. Additionally, this integrated catalyst delivers a current density of 1.50 A cm-2 at 0.6 V in the hydrogen-air fuel cell and achieves a power density of 980 mW cm-2. Comprehensive investigations demonstrate that the synergistic contribution of components and structure in the platinum-carbon integrated catalyst is responsible for the high-efficiency ORR in fuel cells.

Designing Robust Support for Pt Alloy Nanoframes with Durable Oxygen Reduction Reaction Activity.

Polymer electrolyte membrane fuel cells are appealing to resolve the environmental and energy issues but are still heavily inhibited by the dilemma of fabricating effective and durable electrocatalysts for oxygen reduction reaction (ORR). In this work, highly open Pt3Cu nanoframes and one-dimensional, hollow titanium nitride architectures are both successfully explored and implemented as the new system to replace the traditional Pt-carbon motif. The ORR performance of the obtained electrocatalyst shows specific and mass activities of 5.32 mA cm-2 and 2.43 A mgPt-1, respectively, which are 14.4 and 11.6 times higher than those of the commercial Pt/C. Notably, the novel catalyst also exhibits high stability and a much slower performance degradation than that of the benchmarked Pt3Cu/C with the same durability testing procedures. The comprehensive data confirm that the new type of catalyst possesses a high charge transfer during the ORR process, and the unique structure and synergistic effects between anchored Pt and the support mainly contributes to the high stability. This work provides a strategic method for designing an effective ORR electrocatalyst with desirable stability.

Rational Design of an Ionic Liquid-Based Electrolyte with High Ionic Conductivity Towards Safe Lithium/Lithium-Ion Batteries.

It is a very urgent and important task to improve the safety and high-temperature performance of lithium/lithium-ion batteries (LIBs). Here, a novel ionic liquid, 1-(2-ethoxyethyl)-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR1(2o2) TFSI), was designed and synthesized, and then mixed with dimethyl carbonate (DMC) as appropriate solvent and LiTFSI lithium salt to produce an electrolyte with high ionic conductivity for safe LIBs. Various characterizations and tests show that the highly flexible ether group could markedly reduce the viscosity and provide coordination sites for Li-ion, and the DMC could reduce the viscosity and effectively enhance the Li-ion transport rate and transference number. The electrolyte exhibits excellent electrochemical performance in Li/LiFeO4 cells at room temperature as well as at a high temperature of 60 °C. More importantly, with the addition of DMC, the IL-based electrolyte remains nonflammable and appropriate DMC can effectively inhibit the growth of lithium dendrites. Our present work may provide an attractive and promising strategy for high performance and safety of both lithium and lithium-ion batteries.

Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells.

Development of efficient and robust electrocatalysts is critical for practical fuel cells. We report one-dimensional bunched platinum-nickel (Pt-Ni) alloy nanocages with a Pt-skin structure for the oxygen reduction reaction that display high mass activity (3.52 amperes per milligram platinum) and specific activity (5.16 milliamperes per square centimeter platinum), or nearly 17 and 14 times higher as compared with a commercial platinum on carbon (Pt/C) catalyst. The catalyst exhibits high stability with negligible activity decay after 50,000 cycles. Both the experimental results and theoretical calculations reveal the existence of fewer strongly bonded platinum-oxygen (Pt-O) sites induced by the strain and ligand effects. Moreover, the fuel cell assembled by this catalyst delivers a current density of 1.5 amperes per square centimeter at 0.6 volts and can operate steadily for at least 180 hours.

Photocatalytic debromination of polybrominated diphenyl ethers (PBDEs) on metal doped TiO2 nanocomposites: Mechanisms and pathways.

Nanoparticles of four noble metal doped titanium dioxide (i.e., Pd/TiO2, Ag/TiO2, Pt/TiO2 and Cu/TiO2) were synthesized and investigated for their effectiveness to degrade polybrominated diphenyl ethers (PBDEs) under UV light. All the investigated noble metal additives can greatly enhance the performance of TiO2 to degrade 2,2',4',4'-tetrabromodiphenyl ether (BDE-47). However, the debromination pathways of BDE-47 in Ag/TiO2 and Cu/TiO2 systems are just contrary to those in Pd/TiO2 and Pt/TiO2 systems, and there was an induction period in the former systems but not in the latter systems. The hydrogenation experiment suggests a direct H-atom transfer mechanism in Pd/TiO2 and Pt/TiO2 systems, while in Ag/TiO2 and Cu/TiO2 systems, electron transfer is still the dominant mechanism. Electronic method was applied to explain why BDE-47 exhibit different debromination pathways based on different degradation mechanism. In addition, oxygen was proved to be able to capture both electrons and H atoms, and thus can greatly inhibit the degradation of PBDEs in all investigated systems. Finally, the merit and demerit of each metal doped TiO2 were discussed in detail, including the reactivity, stability and the generation of byproducts. We proposed our study greatly enhance our understanding on the mechanisms of PBDE degradation in various metal doped TiO2 systems.

Tuning the Catalytic Activity of Ir@Pt Nanoparticles Through Controlling Ir Core Size on Cathode Performance for PEM Fuel Cell Application.

Pulse electrochemically synthesis of a series of core-shell structured Ir@Pt/C catalysts in cathode catalysts layer are achieved to fabricate membrane electrode assemblies (MEA) with cathode ultra-low Pt loading. The single cell performance of the MEAs in a H2/air PEMFC greatly rely on the sizes of the Ir core nanoparticle, and the optimum activity occurs with Ir core size of 4.1 nm. The cathode MEA with core-shell structured catalysts with optimal Ir core size exhibited excellent performance in a H2/air single fuel cell, comparable to that of a commercial Pt/C MEA (Johnson Matthey 40% Pt), even though the Pt loading in Ir@Pt was only 40% that of the commercial Pt cathode (0.04 vs. 0.1 mg cm-2). The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy. Based on the characterization results, especially from XPS, we suggest that the effect of Ir core particle size on MEA performance may arise from the interactions between the Pt shell and the Ir core. The XPS results showed that the Ir@Pt/C-300 catalyst has the highest Pt0 fraction among the four tested samples. This work demonstrates the alternative to enhance the cathode performance in single cell of Pt-based core-shell structured catalysts by varying size of the core metal under the Pt shell.

Experimental and theoretical investigations on debromination pathways of polybrominated biphenyls (PBBs) under ultraviolet light.

Polybrominated biphenyls (PBBs) are brominated flame retardants that are widely used in textiles and electronic products. Recently, many researches have been devoted to determining their concentrations in food and in the environment. Yet, their degradation behavior has been less investigated and is not well understood. Here, we have investigated the debromination pathways of PBBs by (UV) light in the case of 2,4,5-tribrominated biphenyl (PBB-29). Our investigation indicates that para-bromine substituent on PBB-29 was preferentially removed. By means of density functional theory (DFT), we found that the energies of the debromination products, the CBr bond length in the excited state (S1), the Mulliken charge of bromine in S1, and the lowest unoccupied molecular orbital (LUMO) in S1 correlated well with the debromination pathways of PBBs. Further, LUMO-based prediction of PBB debromination pathways in S1 suggests that the bromine substituent on all brominated positions (i.e. ortho-, meta- and para-) can be preferentially removed, as the debromination sequence is not based on the brominated position but on the specific brominated arrangement pattern. In addition, reductive debromination preferentially occurs on the benzene ring that has the highest number of bromine substituents. This study provided useful descriptors to predict the debromination pathways of PBBs, and the theoretical result greatly improve our understanding of photolytic debromination of PBBs.