Optimization of Sulfurization Process of Cobalt Sulfide and Nitrogen Doped Carbon Material for Boosting the Oxygen Reduction Reaction Catalytic Activity in Alkaline Medium.
ABSTRACT: In order to reduce fuel cell material cost and promote its application, it is urgent to develop non-noble metal materials to replace platinum as the cathode catalysts in fuel cells. The cobalt sulfide and nitrogen co-doped carbon (S-Co-N/C) materials with metal-organic frameworks as precursors have shown good oxygen reduction reaction (ORR) catalytic activity. Benefiting from the protection of catalytic active sites by sulfur atoms, the stability and alcohol-tolerance of the S-Co-N/C catalyst can be significantly improved. In order to fully understand the effect of the sulfurization process on the properties of the material, zeolite imidazole frameworks (ZIF)-8, and ZIF-67 are used as precursors to prepare a novel material of S-Co-N/C by using a sulfurization-pyrolysis method. Another S-Co-N/C material by using a pyrolysis- sulfurization method is prepared for comparison. The effects of the sulfurization process in the preparation on the morphology, chemical structure, specific surface area, and ORR catalytic activity of the final material are investigated. The experimental results show that the surface of the S-Co-N/C material tends to be rough due to the sulfurization reaction of the metal elements. The porosity of the material is reduced to some extent due to the remaining Zn elements in the final product. Interestingly, some carbon nanotubes are found to be generated on the surface of the S-Co-N/C material because of the synergistic effect of Zn and Co on the carbon material during the pyrolysis process, which is beneficial to accelerate the adsorption of oxygen on the S-Co-N/C surface and the electron transportation during the oxygen reduction reaction. In addition, the generated CoS during the sulfurization process can further protect the Co elements from agglomeration, which can effectively increase the ORR catalytic active sites in the final material. The S-Co-N/C material prepared by the sulfurization-pyrolysis method performs a superior ORR catalytic activity to the one synthesized by the pyrolysis-sulfurization method.
Project description:It is desirable to design nonprecious metal nanocatalysts with high stability and catalytic performance for fine chemicals production. Here, a method is reported for the preparation of cobalt metal and cobalt oxide cores confined within nanoporous nitrogen-doped hollow carbon capsules. Core-shell structured Zn/Co-ZIF@polymer materials are fabricated through a facile coating polymer strategy on the surface of zeolitic imidazolate frameworks (ZIF). A series of hollow carbon capsules with cobalt metal and cobalt oxide are derived from a facile confined pyrolysis of Zn/Co-ZIF@polymer. The hollow Co-CoO<i>x</i>@N-C capsules can prevent sintering and agglomeration of the cobalt nanoparticles and the nanoporous shell allows for efficient mass transport. The specific surface area and Co particle size are optimized through finely tuning the original Zn content in ZIF particles, thus enhancing overall catalytic activity. The yolk-shell structured Zn<sub>4</sub>Co<sub>1</sub>O<sub>x</sub>@carbon hollow capsules are shown to be a highly active and selective catalyst (selectivity >99%) for hydrogenation of nitrobenzene to aniline. Furthermore, Zn<sub>4</sub>Co<sub>1</sub>O<sub>x</sub>@carbon hollow particles show superior catalytic stability, and no deactivation after 8 cycles of reaction. The hollow Co-CoO<i>x</i>@N-C capsules may shed light on a green and sustainable catalytic process for fine chemicals production.
Project description:N-doped metal materials with enhanced stability and abundant porosity have attracted tremendous attention in catalytic reactions. Herein, a simple solvothermal approach was demonstrated to significantly enlarge the pore dimension of conventional microporous zeolitic imidazolate framework (ZIF) incorporated with two kinds of central metals (Co, Zn), while maintaining the original ZIF crystal morphology. Upon further pyrolysis, the resulting mesoporous Co-Zn/N-C material could possess the highly dispersed metal particle on the N-doped carbon, with satisfactory pore volume and surface area. The partial vaporization of Zn and the stabilizing effect of N, illustrated by XRD, HRTEM, HAADF-STEM with mapping, SEM, Raman Spectrum, BET, and TGA, were able to remarkably increase the accessibility of substrate toward active sites and prevent the aggregation of metal particles, respectively. Under mild reaction conditions, the N-stabilized Co-Zn/N-C exhibited good activity and selectivity in transfer hydrogenation of various nitro compounds to corresponding amines, where a synergistic role among Co, Zn, and N was responsible for its superior performance to other tested catalysts. In addition, the N-doped non-noble metal/carbon heterogeneous catalyst was fairly stable and could be reused several times without obvious deactivation.
Project description:The development of bi-functional electrocatalyst with high catalytic activity and stable performance for both oxygen evolution/reduction reactions (OER/ORR) in aqueous alkaline solution is key to realize practical application of zinc-air batteries (ZABs). In this study, we reported a new porous nano-micro-composite as a bi-functional electrocatalyst for ZABs, devised by the in situ growth of metal-organic framework (MOF) nanocrystals onto the micrometer-sized Ba<sub>0.5</sub>Sr<sub>0.5</sub>Co<sub>0.8</sub>Fe<sub>0.2</sub>O<sub>3</sub> (BSCF) perovskite oxide. Upon carbonization, MOF was converted to porous nitrogen-doped carbon nanocages and ultrafine cobalt oxides and CoN<sub>4</sub> nanoparticles dispersing inside the carbon nanocages, which further anchored on the surface of BSCF oxide. We homogeneously dispersed BSCF perovskite particles in the surfactant; subsequently, ZIF-67 nanocrystals were grown onto the BSCF particles. In this way, leaching of metallic or organic species in MOFs and the aggregation of BSCF were effectively suppressed, thus maximizing the number of active sites for improving OER. The BSCF in turn acted as catalyst to promote the graphitization of carbon during pyrolysis, as well as to optimize the transition metal-to-carbon ratio, thus enhancing the ORR catalytic activity. A ZAB fabricated from such air electrode showed outstanding performance with a potential gap of only 0.83 V at 5 mA cm<sup>-2</sup> for OER/ORR. Notably, no obvious performance degradation was observed for the continuous charge-discharge operation for 1800 cycles over an extended period of 300 h.
Project description:Heteroatom doping is considered an efficient strategy when tuning the electronic and structural modulation of catalysts to achieve improved performance towards renewable energy applications. Herein, we synthesized a series of carbon-based hierarchical nanostructures through the controlled pyrolysis of Co-MOF (metal organic framework) precursors followed by in situ phosphidation. Two kinds of catalysts were prepared: metal nanoparticles embedded in carbon nanotubes, and metal nanoparticles dispersed on the carbon surface. The results proved that the metal nanoparticles embedded in carbon nanotubes exhibit enhanced ORR electrocatalytic performance, owed to the enriched catalytic sites and the mass transfer facilitating channels provided by the hierarchical porous structure of the carbon nanotubes. Furthermore, the phosphidation of the metal nanoparticles embedded in carbon nanotubes (P-Co-CNTs) increases the surface area and porosity, resulting in faster electron transfer, greater conductivity, and lower charge transfer resistance towards ORR pathways. The P-Co-CNT catalyst shows a half-wave potential of 0.887 V, a Tafel slope of 67 mV dec−1, and robust stability, which are comparatively better than the precious metal catalyst (Pt/C). Conclusively, this study delivers a novel path for designing multiple crystal phases with improved catalytic performance for energy devices.
Project description:Pyrolyzed iron-based platinum group metal (PGM)-free nitrogen-doped single site carbon catalysts (Fe-NC) are possible alternatives to platinum-based carbon catalysts for the oxygen reduction reaction (ORR). Bimetallic PGM-free M<sub>1</sub>M<sub>2</sub>-NC catalysts and their active sites, however, have been poorly studied to date. The present study explores the active accessible sites of mono- and bimetallic Fe-NC and FeNi-NC catalysts. Combining CO cryo chemisorption, X-ray absorption and <sup>57</sup>Fe Mössbauer spectroscopy, we evaluate the number and chemical state of metal sites at the surface of the catalysts along with an estimate of their dispersion and utilization. Fe L<sub>3,2</sub>-edge X-ray adsorption spectra, Mössbauer spectra and CO desorption all suggested an essentially identical nature of Fe sites in both monometallic Fe-NC and bimetallic FeNi-NC; however, Ni blocks the formation of active sites during the pyrolysis and thus causes a sharp reduction in the accessible metal site density, while with only a minor direct participation as a catalytic site in the final catalyst. We also use the site density utilization factor, <i>ϕ</i> <sub>SD<sub>surface/bulk</sub></sub> , as a measure of the metal site dispersion in PGM-free ORR catalysts. <i>ϕ</i> <sub>SD<sub>surface/bulk</sub></sub> enables a quantitative evaluation and comparison of distinct catalyst synthesis routes in terms of their ratio of accessible metal sites. It gives guidance for further optimization of the accessible site density of M-NC catalysts.
Project description:Pyrolyzing metal-organic frameworks (MOFs) typically yield composites consisting of metal/metal oxide nanoparticles finely dispersed on carbon matrices. The blend of pseudocapacitive metal oxides and conductive metals, as well as highly porous carbon networks, offer unique opportunities to obtain supercapacitor electrodes with mutually high capacitances and excellent rate capabilities. Herein, we demonstrate nitrogen-doped carbon nanocuboid arrays grown on carbon fibers and incorporating cobalt metal and cobalt metal oxides. This composite was synthesized via pyrolysis of a chemical bath deposited MOF, cobalt-containing zeolite imidazole framework (Co-ZIF). The active materials for charge storage are the cobalt oxide and nitrogen-doped carbon. Additionally, the Co metal and the nanoporous carbon network facilitated electron transport and the rich nanopores in each nanocuboid shortened ion diffusion distance. Benefited from these merits, our Co-ZIF-derived electrode delivered an areal capacitance of 1177 mF cm<sup>-2</sup> and excellent cycling stability of ~94% capacitance retained after 20,000 continuous charge-discharge cycles. An asymmetric supercapacitor prototype having the Co-ZIF-derived hybrid material (positive electrode) and activated carbon (negative electrode) achieved a maximal volumetric energy density of 1.32 mWh cm<sup>-3</sup> and the highest volumetric power density of 376 mW cm<sup>-3</sup>. This work highlights the promise of metal-metal oxide-carbon nanostructured composites as electrodes in electrochemical energy storage devices.
Project description:Exploring efficient and cost-effective catalysts to replace precious metal catalysts, such as Pt, for electrocatalytic oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) holds great promise for renewable energy technologies. Herein, we prepare a type of Co catalyst with single-atomic Co sites embedded in hierarchically ordered porous N-doped carbon (Co-SAS/HOPNC) through a facile dual-template cooperative pyrolysis approach. The desirable combination of highly dispersed isolated atomic Co-N4 active sites, large surface area, high porosity, and good conductivity gives rise to an excellent catalytic performance. The catalyst exhibits outstanding performance for ORR in alkaline medium with a half-wave potential (E 1/2) of 0.892 V, which is 53 mV more positive than that of Pt/C, as well as a high tolerance of methanol and great stability. The catalyst also shows a remarkable catalytic performance for HER with distinctly high turnover frequencies of 0.41 and 3.8 s-1 at an overpotential of 100 and 200 mV, respectively, together with a long-term durability in acidic condition. Experiments and density functional theory (DFT) calculations reveal that the atomically isolated single Co sites and the structural advantages of the unique 3D hierarchical porous architecture synergistically contribute to the high catalytic activity.
Project description:Here we report new porous carbon materials obtained by 3D printing from photopolymer compositions with zinc- and nickel-based metal-organic frameworks, ZIF-8 and Ni-BTC, followed by high-temperature pyrolysis. The pyrolyzed materials that retain the shapes of complex objects contain pores, which were produced by boiling zinc and magnetic nickel particles. The two thus provided functionalities-large specific surface area and ferromagnetism-that pave the way towards creating heterogenous catalysts that can be easily removed from reaction mixtures in industrial catalytic processes.
Project description:There is currently a pursuit of synthetic approaches for designing porous carbon materials with selective CO<sub>2</sub> capture and/or excellent energy storage performance that significantly impacts the environment and the sustainable development of circular economy. In this study we prepared a new bio-based benzoxazine (AP-BZ) in high yield through Mannich condensation of apigenin, a naturally occurring phenol, with 4-bromoaniline and paraformaldehyde. We then prepared a PA-BZ porous organic polymer (POP) through Sonogashira coupling of AP-BZ with 1,3,6,8-tetraethynylpyrene (P-T) in the presence of Pd(PPh<sub>3</sub>)<sub>4</sub>. In situ Fourier transform infrared spectroscopy and differential scanning calorimetry revealed details of the thermal polymerization of the oxazine rings in the AP-BZ monomer and in the PA-BZ POP. Next, we prepared a microporous carbon/metal composite (PCMC) in three steps: Sonogashira coupling of AP-BZ with P-T in the presence of a zeolitic imidazolate framework (ZIF-67) as a directing hard template, affording a PA-BZ POP/ZIF-67 composite; etching in acetic acid; and pyrolysis of the resulting PA-BZ POP/metal composite at 500 °C. Powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller (BET) measurements revealed the properties of the as-prepared PCMC. The PCMC material exhibited outstanding thermal stability (T<sub>d10</sub> = 660 °C and char yield = 75 wt%), a high BET surface area (1110 m<sup>2</sup> g<sup>-1</sup>), high CO<sub>2</sub> adsorption (5.40 mmol g<sup>-1</sup> at 273 K), excellent capacitance (735 F g<sup>-1</sup>), and a capacitance retention of up to 95% after 2000 galvanostatic charge-discharge (GCD) cycles; these characteristics were excellent when compared with those of the corresponding microporous carbon (MPC) prepared through pyrolysis of the PA-BZ POP precursors with a ZIF-67 template at 500 °C.
Project description:Metal-organic frameworks (MOFs) are known for their versatile combination of inorganic building units and organic linkers, which offers immense opportunities in a wide range of applications. However, many MOFs are typically synthesized as multiphasic polycrystalline powders, which are challenging for studies by X-ray diffraction. Therefore, developing new structural characterization techniques is highly desired in order to accelerate discoveries of new materials. Here, we report a high-throughput approach for structural analysis of MOF nano- and sub-microcrystals by three-dimensional electron diffraction (3DED). A new zeolitic-imidazolate framework (ZIF), denoted ZIF-EC1, was first discovered in a trace amount during the study of a known ZIF-CO<sub>3</sub> -1 material by 3DED. The structures of both ZIFs were solved and refined using 3DED data. ZIF-EC1 has a dense 3D framework structure, which is built by linking mono- and bi-nuclear Zn clusters and 2-methylimidazolates (mIm<sup>-</sup> ). With a composition of Zn<sub>3</sub> (mIm)<sub>5</sub> (OH), ZIF-EC1 exhibits high N and Zn densities. We show that the N-doped carbon material derived from ZIF-EC1 is a promising electrocatalyst for oxygen reduction reaction (ORR). The discovery of this new MOF and its conversion to an efficient electrocatalyst highlights the power of 3DED in developing new materials and their applications.