Iron phosphide anchored nanoporous carbon as an efficient electrode for supercapacitors and the oxygen reduction reaction

Inspired by their distinctive properties, transition metal phosphides have gained immense attention as promising electrode materials for energy storage and conversion applications. The introduction of a safe and large-scale method of synthesizing a composite of these materials with carbon is of great significance in the fields of electrochemical and materials sciences. In the current effort, we successfully synthesize an iron phosphide/carbon (FeP/C) with a high specific surface area by the pyrolysis of the gel resulting from the hydrothermal treatment of an iron nitrate–phytic acid mixed solution. In comparison with the blank (P/C), the as-synthesized FeP/C appears to be an efficient electrode material for supercapacitor as well as oxygen reduction reaction (ORR) applications in an alkaline medium in a three-electrode system. In the study of supercapacitors, FeP/C shows areal capacitance of 313 mF cm⁻² at 1.2 mA cm⁻² while retaining 95% of its initial capacitance value after 10 000 cycles, while in the ORR, the synthesized material exhibits high electrocatalytic activity with an onset potential of ca. 0.86 V vs. RHE through the preferred four-electron pathway and less than 6% H₂O₂ production calculated in the potential range of 0.0–0.7 V vs. RHE. The stability is found to be better than those of the benchmark Pt/C (20 wt%) catalyst.

Synthesis of a nanoporous FeP/C material through a two-step method involving hydrothermal and carbonization processes for supercapacitors and the oxygen reduction reaction.     

Organic template-assisted green synthesis of CoMoO4 nanomaterials for the investigation of energy storage properties

Transitional metal oxide nanomaterials are considered to be potential electrode materials for supercapacitors. Therefore, in the past few decades, huge efforts have been devoted towards the sustainable synthesis of metal oxide nanomaterials. Herein, we report a synergistic approach to synthesize spherical-shaped CoMoO₄ electrode materials using an inorganic–organic template via the hydrothermal route. As per the synthesis strategy, the precursor solution was reacted with the organic compounds of E. cognata to tailor the surface chemistry and morphology of CoMoO₄ by organic species. The modified CoMoO₄ nanomaterials revealed a particle size of 23 nm by X-ray diffraction. Furthermore, the synthesized material was scrutinized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, field emission scanning electron microscopy and energy dispersive spectroscopy. The optical band gap energy of 3.6 eV was calculated by a Tauc plot. Gas chromatography-mass spectrometry identified cyclobutanol (C₄H₈O) and octodrine (C₈H₁₉N) as the major stabilizing agents of the CoMoO₄ nanomaterial. Finally, it was revealed that the bioorganic framework-derived CoMoO₄ electrode exhibited a capacitance of 294 F g⁻¹ by cyclic voltammetry with a maximum energy density of 7.3 W h kg⁻¹ and power density of 7227.525 W kg⁻¹. Consequently, the nanofeatures and organic compounds of E. cognata were found to enhance the electrochemical behaviour of the CoMoO₄-fabricated electrode towards supercapacitor applications.

Transitional metal oxide nanomaterials are considered to be potential electrode materials for supercapacitors.     

A high-efficiency oxygen evolution electrode material of a carbon material containing a NiCo bimetal

The preparation of highly efficient, stable, and low-cost electrocatalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) is still a challenge for the development of new energy systems. In this work, a NiCo bimetal loaded on porous carbon (NiCo-C/NF) grown on nickel foam (NF) was obtained via the pyrolysis of a NiCo bimetal MOF (NiCo-MOF/NF) under a nitrogen atmosphere at 500 °C. Compared with NiCo-MOF/NF, NiCo-C/NF had a larger specific surface and uniform mesoporous structure. As an electrocatalyst in the OER, this new type of electrode operated with better stability in an alkaline solution (1.0 mol L⁻¹ KOH), the overpotential when the current density reached 10 mA cm⁻² was only 260 mV, and the electrode also exhibited long-term durability in a stability test for 10 h without significant changes. The excellent activity and stability toward the OER can be attributed to the synergistic effect of the NiCo bimetal and the abundant active sites exposed after the carbonization of NiCo-MOF, which compensated for the defect of the insufficient conductivity of the material and promoted the evolution of oxygen in the catalytic process.

The preparation of highly efficient, stable, and low-cost electrocatalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) is still a challenge for the development of new energy systems.     

Engineering NiCo2S4 nanoparticles anchored on carbon nanotubes as superior energy-storage materials for supercapacitors

Fabricating high-capacity electrode materials toward supercapacitors has attracted increasing attention. Here we report a three-dimensional CNTs/NiCo₂S₄ nanocomposite material synthesized successfully by a facile one-step hydrothermal technique. As expected, a CNTs/NiCo₂S₄ electrode shows remarkable capacitive properties with a high specific capacitance of 890 C g⁻¹ at 1 A g⁻¹. It also demonstrates excellent cycle stability with an 83.5% capacitance retention rate after 5000 cycles at 10 A g⁻¹. Importantly, when assembled into a asymmetric supercapacitor, it exhibits a high energy density (43.3 W h kg⁻¹) and power density (800 W kg⁻¹). The exceptional electrochemical capacity is attributed to the structural features, refined grains, and enhanced conductivity. The above results indicate that CNTs/NiCo₂S₄ composite electrode materials have great potential application in energy-storage devices.

A one-step hydrothermal method was used to successfully synthesize NiCo₂S₄ nanocomposites anchored on carbon nanotubes as excellent energy storage materials for supercapacitors.     

High dispersion and oxygen reduction reaction activity of Co3O4 nanoparticles on platelet-type carbon nanofibers

In this study, platelet-type carbon nanofibers prepared by the liquid phase carbonization of polymers in the pores of a porous anodic alumina template were used to prepare the Co₃O₄/carbon electrocatalysts. For comparison, Co₃O₄ nanoparticles were also deposited on multiwall carbon nanotubes (MWCNTs). Both the nitrogen-free platelet-type carbon nanofibers (pCNFs) and the nitrogen-containing analogue (N-pCNFs) exhibited better dispersion and higher amount of deposited Co₃O₄ nanoparticles compared to the MWCNTs. In addition, many individual Co₃O₄ nanoparticles were deposited separately on pCNF and N-pCNF, whereas aggregated deposition was commonplace on MWCNTs. The results indicated that the side wall of the pCNFs, which consisted of carbon edge planes, was the preferential nucleation site of Co₃O₄ nanoparticles rather than the basal planes of carbon that predominated the surface of the MWCNTs. The oxygen reduction reaction (ORR) activity of the Co₃O₄/pCNF composite in 0.1 mol dm⁻³ KOH solution was better than that of Co₃O₄/MWCNTs. The N-pCNF further enhanced the ORR activity of the Co₃O₄/pCNFs even though the dispersion and supported amount of Co₃O₄ nanoparticles were negligibly affected by the presence of the nitrogen species. Synergistic interactions of the Co₃O₄ nanoparticles with N-doped CNFs contributed to the increased ORR activity.

In this study, platelet-type carbon nanofibers prepared by the liquid phase carbonization of polymers in the pores of a porous anodic alumina template were used to prepare the Co₃O₄/carbon electrocatalysts.     

Highly dispersed Pt nanoclusters supported on zeolite-templated carbon for the oxygen reduction reaction

The formation of highly dispersed Pt nanoclusters supported on zeolite-templated carbon (PtNC/ZTC) by a facile electrochemical method as an electrocatalyst for the oxygen reduction reaction (ORR) is reported. The uniform micropores of ZTC serve as nanocages to stabilize the PtNCs with a sharp size distribution of 0.8–1.5 nm. The resultant PtNC/ZTC exhibits excellent catalytic activity for the ORR due to the small size of the Pt clusters and high accessibility of the active sites through the abundant micropores in ZTC.

Electrochemically synthesized highly dispersed Pt nanoclusters (PtNCs) stabilized by the nanocages of zeolite-templated carbon (ZTC) exhibit excellent electrocatalytic performance toward the oxygen reduction reaction.

Platinum (Pt) is currently considered one of the best electrocatalysts for the oxygen reduction reaction (ORR), which occurs at the cathode of a fuel cell and is the key process determining the overall performance.^1–5 However, the high cost and scarcity of Pt limit its wide commercialization in this field. According to the US Department of Energy, the total Pt loading is required to be below 0.125 mg cm⁻², in contrast to a presently used Pt loading of 0.4 mg cm⁻² or more for fuel cell application.⁴ Therefore, reducing the Pt loading without loss or with an improvement of the cathode performance has received significant interest in electrocatalytic research for fuel cell systems.^6–10 In this regard, reducing the size of Pt particles to a nanocluster scale (size < 2 nm) and maximizing the Pt dispersion may offer an efficient way to achieve maximum utilization of the Pt electrocatalyst with appropriate consumption.^4,11–15The size of nanomaterials generally plays a critical role in controlling the physical and chemical properties for catalytic applications.^16–20 With a decrease in the particle size to the nanoscale, quantum size effects are induced, which alter the surface energy of the material due to unsaturated coordination and change in the energy level of the d orbital of metal atoms, leading to spatial localization of the electrons.^17–20 This size-induced effect on the electronic structures at the active sites modifies the capability of binding the reactant molecules in catalytic reactions, thereby altering the activity of the nanocatalyst.²⁰ When the particle contains a few to several dozens of atoms with sizes, ranging from sub-nanometer to 2 nm often termed as nanocluster that bridges nanoparticle and a single atom.²¹ However, the Pt single atom is not an appropriate electrocatalyst for the ORR in a fuel cell system as the fast four-electron (4e⁻) pathway for the reduction of O₂ to H₂O requires at least two neighboring Pt atoms.^22,23 Anderson''s group demonstrated that the ratio between the production of H₂O (product of 4e⁻ process) and H₂O₂ (2e⁻) in the ORR strongly depends on the number of atoms in the Pt cluster. Typically, it requires more than 14 atoms in a Pt cluster to produce H₂O efficiently through the 4e⁻ pathway of the ORR.²⁴ Therefore, Pt nanoclusters having more than a dozen atoms have proven to be highly efficient ORR electrocatalysts for fuel cell systems.^13–15 Upon decreasing the size of the nanoparticles to a nanocluster, the electronic state and structure are known to be changed, leading to an increase of the catalytic activity in the ORR. Therefore, it is highly desirable to synthesize a Pt nanocluster-based material as an ORR electrocatalyst with high catalytic performance. To date, several synthesis strategies, such as wet-chemical, atomic-layer deposition, and photochemical methods, have been applied for the preparation of well-dispersed Pt nanoclusters on different types of support, such as dendrimer, metal oxide, and carbon materials.^{13–15,25–31}An alternative approach to synthesize Pt nanocluster (PtNC) is the encapsulation of the cluster within nanosized pores, for example, by utilizing microporous (diameters less than 2 nm) carbon materials.³² Among the microporous carbons, zeolite-templated carbon (ZTC) has been attractive for supporting Pt clusters due to its ordered microporous structure.^33–37 ZTC is a potentially promising material as catalyst support as it offers the advantages of extremely large surface area and high electrical conductivity of graphene-like carbon frameworks constituting a three-dimensional (3D) interconnected pore structure.³⁶ Moreover, the micropores of ZTC can serve as nanocages for stabilization of the Pt nanoclusters. Coker et al. used Pt²⁺ ion-exchanged zeolite as a carbon template to synthesize Pt nanoparticles in ZTC with size in a range of 1.3 to 2.0 nm.³³ Recently, atomically dispersed Pt ionic species was synthesized via a simple wet-impregnation method on ZTC containing a large amount of sulfur (17 wt%).²³ Itoi et al. synthesized PtNC consisting of 4–5 atoms and a single Pt atom in ZTC using the organoplatinum complex.³⁷ Although these methods produced Pt nanoclusters with narrow size distribution and atomic dispersion, they required multi-step processes and/or high-temperature treatment (>300 °C). High-temperature treatment often induces the sintering of nanoclusters to aggregated clusters. Therefore, it is highly desirable to develop a simple and low-cost method for the preparation of PtNC supported on ZTC (PtNC/ZTC) for use as an efficient ORR electrocatalyst. The electrochemical reduction approach offers an alternate and efficient route for the synthesis of PtNC in the micropores of ZTC. The electrochemical method is one of the popular ways to prepare electrocatalysts because it is a simple single-step procedure and ensures electrical contact between the nanoparticles and the support.^38,39Herein, we report a facile electrochemical method for the formation of PtNC with a narrow size range of 0.8–1.5 nm supported on ZTC. The resultant PtNC/ZTC shows higher electrocatalytic activities towards ORR compared to that of commercial Pt/C. Here, ZTC plays two important roles: (i) it provides nanocages to stabilize the PtNC and (ii) it accelerates the ORR activity by enhancing the accessibility of active sites through its abundant micropores. Fig. 1a shows a schematic representation of the typical electrochemical synthesis of PtNC/ZTC. In the first step, ZTC was impregnated with a Pt-precursor dissolved in a water–ethanol mixture. As ZTC possess ordered micropores (Fig. S1a^†) with high Brunauer–Emmett–Teller (BET) surface area of 3400 m² g⁻¹ (vide infra), the uniform adsorption and anchorage of PtCl₆²⁻ ions into the micropores of ZTC was favored. After impregnating and drying, the resultant ZTC–PtCl₆²⁻ was mixed with water–ethanol and Nafion to make the ink for the preparation of the electrode. Using the prepared electrode, a potential of 0.77 V vs. reversible hydrogen electrode (RHE) (Fig. 1b) was applied followed by potential cycling between 1.12 to −0.02 V vs. RHE until the cyclic voltammogram was stabilized. The Pt content of PtNC/ZTC was determined to be ∼10 wt% (Fig. S2^†) by thermogravimetric analysis (TGA). The obtained PtNC/ZTC was electrochemically characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The cyclic voltammogram (Fig. 1c) after potential cycling in fresh KOH electrolyte shows the characteristic Pt peaks corresponding to hydrogen adsorption and desorption. The Nyquist plots (Fig. 1d) demonstrate that PtNC/ZTC has lower electrolyte resistance (42 Ω) than that of ZTC (70 Ω), implying an improvement in the conductivity of ZTC by the presence of PtNC. Due to the increase in the conductivity, PtNC/ZTC could facilitate the electron transfer more effectively than ZTC, enhancing its electrocatalytic activity.Open in a separate windowFig. 1(a) Illustration for the formation of PtNC/ZTC:Pt-precursor was impregnated into ZTC micropores, and then a potential (0.77 V vs. RHE) was exerted on the ZTC–PtCl₆²⁻ composite in a 0.1 M KOH solution to form PtNC/ZTC (b) Chronoamperometric response of ZTC–PtCl₆²⁻ at a constant potential of 0.77 V (vs. RHE) in 0.1 M KOH electrolyte. (c) Cyclic voltammogram of PtNC/ZTC in a fresh 0.1 M KOH at a scan rate of 20 mV s⁻¹. (d) Nyquist plots of ZTC and PtNC/ZTC in 0.1 M KOH. Fig. 2a and b show images from aberration-corrected scanning transmission electron microscope (STEM) with high-angle annular dark-field (HAADF). The HAADF-STEM images exhibit the typical morphology of the final product (PtNC/ZTC) after electrochemical reduction. As shown in Fig. 2a, it is very clear that isolated PtNCs are uniformly dispersed in ZTC. These PtNCs have a homogeneous distribution with a narrow size range (0.8–1.5 nm, Fig. 2b). On further magnification, the STEM image shows a cluster-like structure of Pt (Fig. 2c). The STEM image of selected PtNC (Fig. 2d) reveals that it consists of ∼20 atoms. The number of atom content in PtNC was further determined by matrix-assisted laser-desorption-ionization time-of-flight (MALDI-TOF) mass spectrometry using trans-2-[3-(4-test-butylphenyl)-2-methyl-2-propenylidene]malononitrile as the matrix.^40,41 As shown in Fig. S3,^† MALDI-TOF measurement produces a mass spectra with a predominant peak centered at ∼3700 Da corresponding to the Pt₁₉ cluster. The TEM image (Fig. S4 a and b^†) validates the formation of PtNC with an average size of 0.9 nm. In addition, the energy dispersive X-ray spectrometer (EDS) mapping images clearly shows the uniform dispersion of Pt nanocluster in ZTC (Fig. S4c^†). The X-ray powder diffraction (XRD) pattern (Fig. 2e) of PtNC/ZTC showed three broad peaks associated with small size metallic Pt corresponds to (111), (200), and (311) planes (Fig. 2e, inset), along with peaks of ZTC at 2θ = 7.8° and 14.9° corresponding to the ordered microporous structure. Along with the structural analysis, the porous texture of PtNC/ZTC was examined by Ar adsorption (Fig. 2f). PtNC/ZTC had a high BET surface area of 2360 m² g_ZTC⁻¹, which is 1.4 times lower than that of pristine ZTC (3400 m² g_ZTC⁻¹). The decrease in Ar adsorption capacity after the formation of PtNC in ZTC is interpreted as a result of the filling of ZTC micropores by PtNC. This micropore filling was confirmed in the pore size distributions of the pristine ZTC and the metal-loaded carbon (inset of Fig. 2f). The X-ray photoelectron spectroscopy (XPS) results reveal the signature of Pt in ZTC (Fig. S5^†). The elemental survey (Fig. S5a^†) shows the signature of C 1s, O 1s, F 1s (Nafion), and Pt 4f. The chemical nature of Pt in PtNC/ZTC was inspected by a detailed Pt 4f XPS analysis. The deconvoluted Pt 4f XPS spectra (Fig. S5b^†) reveals the presence of both metallic and ionic Pt species. The peaks observed at 71.0 (4f_7/2) and 74.2 (4f_5/2) eV correspond to metallic Pt whereas the other peaks positioned at 72.6 (4f_7/2) and 76.0 (4f_5/2) are attributed to Pt²⁺ and the peaks at 74.9 (4f_7/2) and 77.8 (4f_5/2) eV are attributed to Pt⁴⁺ originating from the surface oxidation of metallic Pt.⁴²Open in a separate windowFig. 2(a–d) Representative spherical aberration-corrected HAADF-STEM images of PtNC/ZTC at various magnifications. (e) XRD pattern of PtNC/ZTC and (f) Ar adsorption–desorption isotherms of ZTC and PtNC/ZTC. Inset in (e) shows a 30 times magnified high-angle region of XRD of PtNC/ZTC. Inset in (f) shows the pore size distributions of the ZTC and PtNC/ZTC.The formation of narrow sized PtNC by the electrochemical method can be ascribed to the stabilization of PtNC in the ZTC micropores, which serve as cages to impose a spatial limitation on the size of the Pt clusters. For comparison, Pt supported on ZTC was also prepared by the conventional incipient wetness impregnation and subsequent H₂-reduction at high temperature (300 °C). The Pt obtained by this incipient wetness impregnation method shows the formation of Pt nanoparticles on the exterior surface of ZTC (PtNP/ZTC) (Fig. S6^†). The formation of larger Pt nanoparticles is due to the sintering at high temperature, showing that even ZTC micropores could not prevent the aggregation of PtNCs at high temperatures. Fig. 3 shows the electrochemical ORR activity of PtNC/ZTC using linear sweep voltammetry (LSV) technique on a rotating disc electrode (RDE) in a 0.1 M KOH solution saturated with O₂ at a scan rate of 5 mV s⁻¹. The ORR activity of ZTC (without PtNC) was measured for comparison as well. As shown in Fig. 3a, PtNC/ZTC exhibited higher diffusion limiting current density and higher positive onset and half-wave potential compared to ZTC alone, indicating that PtNC is the active center for the ORR. To investigate the effect of the Pt loading amount on the ORR activity, PtNC/ZTC with various Pt loadings, 2–20 wt%, was used for the measurement of LSV at 1600 rpm. With an increase in Pt content, both the onset and half-wave potential shifted towards more positive potential up to 10 wt% loading of Pt (Fig. 3a and S7^†). Upon further increase of loading of Pt on ZTC to 20 wt%, both the onset and half-wave potential of PtNC/ZTC shifted towards less positive potential along with a slight decrease in the diffusion limiting current density (Fig. 3a). The decrease in the ORR activity of PtNC/ZTC at high loading of Pt (20 wt%) was attributed to the decrease in the electrochemically active surface area (Fig. S8^†) and decrease in the specific surface area (Fig. S9^†). The STEM image clearly shows that the aggregated Pt clusters were formed on the exterior surface of ZTC at 20 wt% loading of Pt (Fig. S10c^†), blocking the accessibility of active sites. Therefore, PtNC/ZTC with the optimum loading of 10 wt% of Pt leads to superior ORR activity with a high positive onset potential of 0.99 V, which is similar to commercial Tanaka Pt/C (Pt/C-TKK) (Fig. 3b), and a half-wave potential of 0.87 V, which is ∼10 mV more positive than that of commercial Pt/C-TKK (0.86 V) (Fig. 3b). Compared to the case of PtNC/ZTC, both the onset and half-wave potential of PtNP/ZTC prepared by the conventional incipient wetness impregnation and subsequent H₂-reduction with the same loading of Pt exhibited a less positive value (Fig. S11^†). The poorer activity of PtNP/ZTC is due to the blockage of active sites by larger PtNPs formed on the exterior surface of ZTC (Fig. S6^†).Open in a separate windowFig. 3(a) RDE ORR polarization curves of PtNC/ZTC with different mass loading of Pt. (b) Comparison of PtNC/ZTC (PtNC_10%/ZTC) with commercial Pt/C-TKK at the same loading of 40 μg_Pt cm⁻². (c) RDE ORR polarization curves of PtNC/ZTC at different rotation speeds. Inset in (c) shows the corresponding K–L plots at different potentials. (d) Represents the kinetic current density values of Pt/C-TKK and PtNC/ZTC at the potential of 0.8 V vs. RHE.To investigate the kinetics of the ORR activity of PtNC/ZTC, LSV measurements were performed with RDE at different rotating rates (Fig. 3c), and the kinetics was analyzed using a Koutecký–Levich (K–L) plot (Fig. 3c, inset). From Fig. 3c, it was observed that the current density increases with the increasing speed of rotation of the electrode, which is characteristic of a diffusion-controlled reaction. The corresponding linear K–L plots (Fig. 3c, inset) with a similar slope at different potentials reveal that the number of transferred electrons was ∼4, indicating that O₂ is directly reduced to OH⁻ and the ORR is dominated by the H₂O₂-free 4e⁻ pathway. To estimate the amount of produced peroxide ion, rotating ring-disc electrode (RRDE) measurement was performed and the produce peroxide ion calculated from RRDE curve was < 4% (Fig. S12^†). The kinetic current density (J_k) obtained from K–L plot at the potential of 0.8 V (Fig. 3d) for PtNC/ZTC (J_k = 50 mA cm⁻²) is 2.2 times higher than that of commercial Pt/C-TKK (J_k = 22 mA cm⁻²).As Pt-based electrocatalysts are known to be highly active in an acidic medium, the ORR activity of PtNC/ZTC in O₂-saturated 0.1 M HClO₄ was also evaluated by comparing it with that of commercial Pt/C-TKK with the same loading of Pt on the electrode surface using RDE at a scan rate of 5 mV s⁻¹. The PtNC/ZTC-based electrode exhibited ORR activity with an onset potential of 0.96 V (Fig. 4), which is close to that of Pt/C-TKK (0.98 V), and half-wave potentials of 0.84 V, which is 20 mV more positive than that of Pt/C-TKK (0.82 V). PtNC/ZTC showed a slightly higher diffusion-limiting current density of ∼5.9 mA cm⁻² (0.4–0.7 V) compared with that of the Pt/C-TKK catalyst (∼5.6 mA cm⁻²). The kinetics of the ORR in an acidic medium was further analyzed using RDE at different rotation rates (Fig. S13^†) and it was observed that the current density increases with the increasing speed of rotation of the electrode, as in the case of the alkaline medium. The number of electron involved and the amount of produced H₂O₂ estimated by RRDE measurement were ∼4 and < 5%, respectively (Fig. S14^†). The mass activity of PtNC/ZTC obtained using the mass transport corrected kinetic current at 0.8 V is 0.15 A mg⁻¹, which is 3.2 times higher than that of Pt/C-TKK (0.046 A mg⁻¹).Open in a separate windowFig. 4(a) RDE ORR polarization curves at 1600 rpm and (b) mass activity at 0.8 V of PtNC/ZTC and Pt/C-TKK in 0.1 M HClO₄.Furthermore, the methanol tolerance of PtNC/ZTC was assessed by intentionally adding methanol to the oxygen saturated electrolyte solution (both in alkaline and acidic media). The commercial Pt/C-TKK was used for comparison as well. The peak current densities for methanol oxidation with PtNC/ZTC were ∼2.8 and ∼3 times lower than that of Pt/C-TKK in alkaline (Fig. 5a) and acidic (Fig. 5b) media, respectively. These results indicate that PtNC/ZTC has much higher tolerance towards methanol than Pt/C-TKK does. This higher methanol tolerance of PtNC/ZTC can be attributed to the small size of the Pt cluster, which may not be sufficient to catalyze the oxidation of methanol efficiently, as the oxidation of methanol requires Pt ensemble sites.⁴³Open in a separate windowFig. 5ORR polarization curves of PtNC/ZTC and Pt/C-TKK in the absence (solid line) and presence (dotted line) of 0.1 M of CH₃OH at a rotation rate of 1600 rpm in (a) alkaline and (b) acid media.The durability of PtNC/ZTC was also investigated by the amperometric technique. The test was performed at a constant voltage of the half-wave potential in an O₂-saturated alkaline medium and at 0.7 V in an O₂-saturated acidic medium at a rotation rate of 1600 rpm (Fig. S15a and b^†). The durability of the PtNC/ZTC catalyst in the alkaline medium was higher than that of Pt/C-TKK, exhibiting a 30% decrease compared to a 40% decrease of Pt/C-TKK in 5.5 h of ORR operation (Fig. S15a^†). The higher durability of PtNC/ZTC compared to Pt/C-TKK in the alkaline medium may be due to the stabilization of PtNC by pore entrapment. In the acidic medium, however, PtNC/ZTC exhibited a 54% decrease in the initial current after 5.5 h of operation while a 33% decrease was observed in the case of Pt/C-TKK (Fig. S15b^†). The decrease in ORR activity in the acidic medium may be due to the leaching out of tiny Pt nanoclusters in acid electrolyte from the ZTC micropores. To understand the decrease in the ORR durability with time, STEM measurements of PtNC/ZTC after 5.5 h of ORR operation were performed. In the alkaline medium, the STEM image of post-ORR PtNC/ZTC shows a slight change in the size of PtNC (Fig. S15c^†) while the STEM image of PtNC/ZTC after ORR in the acidic medium exhibited sintering of PtNC into large particles with an average size of 30 nm (Fig. S15d^†), resulting in a decrease of the ORR activity. In the alkaline medium, the decrease in ORR activity with time may be due to the oxidation of the ZTC support in KOH.⁴⁴We attributed the excellent ORR activity of PtNC/ZTC to the interplay between the following: (1) the structure of the Pt cluster possessing a high ratio of surface atoms that benefits the surface reactions,^45–47 (2) the microporous 3D graphene-like structure of the ZTC support that enables easy access of O₂ and electrolyte molecules to the active sites,⁴⁸ and (3) the high conductivity and large accessible surface area of ZTC that facilitates the electron transfer.^49–51     

High-performance electrocatalyst based on polyazine derived mesoporous nitrogen-doped carbon for oxygen reduction reaction

Nitrogen-doped porous carbon materials have high potential in metal-free electrocatalysts, which is essential for several renewable energy conversion systems. Herein, we report a convenient and environment-friendly method to fabricate a nitrogen doped mesoporous carbon (NMC) using a nonionic surfactant of Pluronic F127 micelles as the template and a Schiff-base polymer (polyazine) as the precursor. The synthesized NMCs were of spheric morphology and mesoporous structures with surface area up to 1174 m² g⁻¹ and high level of nitrogen (2.9–19 at%) and oxygen (4.9–7.4 at%) simultaneously doped. The electrochemical data of NMCs were analyzed in the context of the BET and XPS information. A correlation between ORR activity and the pyridinic-N was found. The NMC-700 demonstrate the highest electrocatalytic activity for ORR among the studied materials, which can be ascribed to the reasonable surface area and mesoporous structure, as well as the most abundant touchable pyridinic-N, thus providing more effective active sites for the oxygen reduction. In comparsion to the control sample, the NMC-700 provides the ORR electrocatalytic activity approximate to that of commercial Pt/C catalyst with a highly long-term stability.

Nitrogen-doped porous carbon materials have high potential in metal-free electrocatalysts, which is essential for several renewable energy conversion systems.     

Tubular g-C3N4/carbon framework for high-efficiency photocatalytic degradation of methylene blue

The preparation of high-efficiency, pollution-free photocatalysts for water treatment has always been one of the research hotspots. In this paper, a carbon framework formed from waste grapefruit peel is used as the carrier. A simple one-step chemical vapor deposition (CVD) method allows tubular g-C₃N₄ to grow on the carbon framework. Tubular g-C₃N₄ increases the specific surface area of bulk g-C₃N₄ and enhances the absorption of visible light. At the same time, the carbon framework can effectively promote the separation and transfer of charges. The dual effects of static adsorption and photodegradation enable the g-C₃N₄/carbon (CNC) framework to quickly remove about 98% of methylene blue within 180 min. The recyclability indicates that the tubular g-C₃N₄ can stably exist on the carbon framework during the photodegradation process. In the dynamic photocatalytic test driven by gravity, roughly 77.65% of the methylene blue was degraded by the CNC framework. Our work provides an attractive strategy for constructing a composite carbon framework photocatalyst based on the tubular g-C₃N₄ structure and improving the photocatalytic performance.

Tubular g-C₃N₄ grown on a carbon framework increased the surface area of bulk g-C₃N₄, enhanced the absorption of visible light and promoted the photocatalytic performance.     

MOF-derived ZnCo2O4 porous micro-rice with enhanced electro-catalytic activity for the oxygen evolution reaction and glucose oxidation

A porous ZnCo₂O₄ micro-rice like microstructure was synthesized via calcination of a Zn–Co MOF precursor at an appropriate temperature. The as-prepared ZnCo₂O₄ sample presented good electrocatalytic oxygen evolution reaction performance with a small overpotential (η₁₀ = 389 mV) and high stability in basic electrolyte. Furthermore, in basic medium, the as-synthesized ZnCo₂O₄ micro-rice also showed good electrocatalytic activity for glucose oxidation. A ZnCo₂O₄ micro-rice modified glass carbon electrode may be used as a potential non-enzymatic glucose sensor. The excellent electrocatalytic OER and glucose oxidation performances of ZnCo₂O₄ might be attributed to the unique porous structure formed by the nanoparticles. The porous architecture of the micro-rice can provide a large number of electrocatalytically active sites and high electrochemical surface area (ECSA). The result may offer a new way to prepare low-cost and high performance oxygen evolution reaction and glucose oxidation electrocatalysts.

A porous ZnCo₂O₄ micro-rice like microstructure was synthesized via calcination of a Zn–Co MOF precursor at an appropriate temperature.     

A facile synthesis of hierarchically porous carbon derived from serum albumin by a generated-templating method for efficient oxygen reduction reaction

Hierarchically porous carbons (HPCs), with large specific surface area, abundant porous channels and adequate anchor points, act as one type of ideal carbon supports for the preparation of single-atom electrocatalysts. In this study, the blood plasma-derived HPC with an interconnected porous framework is constructed via a generated-template method, with the formation of ZnS nanoparticles from the abundant disulfide bonds (–S–S–) in serum albumin. After the thermal activation with heme-containing molecules (also from the bovine-blood biowaste), the HPC exhibits high-exposure and low-spin-state Fe(ii)–N₄ atomic active sites, and thereby presents a superior oxygen reduction reaction activity (the half wave potential of 0.87 V) and excellent stability (a 4 mV negative shift after 3000 potential cycles), even comparable with the benchmark Pt/C. This work delivers a new insight into the design and synthesis of porous carbons and carbon-based electrocatalysts to develop bio-derived materials in the field of clean energy conversion and storage.

A high-performance Fe–N–HPC electrocatalyst derived from bovine blood.     

Controllable synthesis of N-doped carbon nanohorns: tip from closed to half-closed,used as efficient electrocatalysts for oxygen evolution reaction

The development of efficient, cost-effective and stable N-doped carbon material with catalytic activity as an excellent catalyst for the oxygen evolution reaction (OER) is critical for renewable energy systems. In this study, the unique tip-half-closed N-doped carbon nanohorns (THC-N-CNHs) were firstly produced by the positive pressure-assisted arc discharge method using N₂ as the nitrogen source. Benefitting from the novel tip-half-closed structure and sufficient porosity, the specific surface area (SSA) of THC-N-CNHs is calculated to be 670 m² g⁻¹ without any further treatment, which is three times larger than that of traditional tip-closed CNHs. More importantly, the content of nitrogen can achieve ∼1.98 at% with noticeable pyridinic-N enrichment, increasing the number of active sites for the OER. Furthermore, the three-dimensional spherical feature and the unique pore structure for THC-N-CNHs lead to the fast transportation of electrons, and facile release of the evolved O₂ bubbles during the OER process. Therefore, THC-N-CNHs exhibit excellent electrocatalytic activity toward the OER, with an overpotential of 328 mV at 10 mA cm⁻², which is superior to that of most N-doped carbon material-based electrocatalysts. Meanwhile, the resulting catalyst also shows excellent durability after long-term cycling. Finally, we emphasize that THC-N-CNHs can be promising candidates as cheap, industrially scalable catalytic scaffolds for OER application.

The unique tip-half-closed N-doped carbon nanohorns were firstly produced with sufficient porosity and noticeable pyridinic-N, exhibiting excellent OER performance.     

One-step sulfuration synthesis of hierarchical NiCo2S4@NiCo2S4 nanotube/nanosheet arrays on carbon cloth as advanced electrodes for high-performance flexible solid-state hybrid supercapacitors

To obtain high-performance hybrid supercapacitors (HSCs), a new class of battery-type electrode materials with hierarchical core/shell structure, high conductivity and rich porosity are needed. Herein, we propose a facile one-step sulfuration approach to achieve the fabrication of hierarchical NiCo₂S₄@NiCo₂S₄ hybrid nanotube/nanosheet arrays (NTSAs) on carbon cloth, by taking hydrothermally grown Ni–Co precursor@Ni–Co precursor nanowire/nanosheet arrays (NWSAs) as the starting templates. The optimized electrode of NiCo₂S₄@NiCo₂S₄ hybrid NTSAs demonstrates an enhanced areal capacity of 245 μA h cm⁻² at 2 mA cm⁻² with outstanding rate capability (73% from 2 to 20 mA cm⁻²) and cycling stability (86% at 10 mA cm⁻² over 3000 cycles). In addition, flexible solid-state HSC devices are assembled by using NiCo₂S₄@NiCo₂S₄ hybrid NTSAs and activated carbon as the positive and negative electrodes, respectively, which manifest a maximum volumetric energy density of 1.03 mW h cm⁻³ at a power density of 11.4 mW cm⁻³, with excellent cycling stability. Our work indicates the feasibility of designing and fabricating core/shell structured metal sulfides through such a facile one-step sulfuration process and the great potential of these materials as advanced electrodes for high-performance HSC devices.

One-step sulfuration synthesis of NiCo₂S₄@NiCo₂S₄ core–shell arrays on carbon cloth.     

All carbon hybrid N-doped carbon dots/carbon nanotube structures as an efficient catalyst for the oxygen reduction reaction

This paper reports the facile and scalable synthesis of hybrid N-doped carbon quantum dots/multi-walled carbon nanotube (CD/CNT) composites, which are efficient alternative catalysts for the oxygen reduction reaction (ORR) in fuel cells. The N-doped CDs for large-scale production were obtained within 5 minutes via a one-step polyol process using ethylenediamine (ED) in the presence of hydrogen peroxide as an oxidizing agent. For comparison, different CDs were also prepared using ethylene glycol (EG) and ethanolamine (EA) in the same manner. Physicochemical characterization suggested the successful formation of a CD(ED)/CNT hybrid without individual CD(ED)s and CNTs. The N-doped CD(ED)/CNT catalyst exhibited excellent electrocatalytic activity in an alkaline solution compared to other composites (CD(EG)/CNT and CD(EA)/CNT). The Tafel slope (−60.9 mV dec⁻¹) and durability (∼9.1% decay over 10 h) for CD(ED)/CNT were superior to high-performance Pt/C catalysts. The electrochemical double-layer capacitance on the CD(ED)/CNT hybrid showed apparent improvement of the active surface area because of N-doping and highly decorated CDs on the CNT wall. These results provide an innovative approach for the potential application of all carbon hybrid structures in electrocatalysis.

The ORR measurements showed that the CD(ED)/CNT catalyst was superior to CD(EG)/CNT and CD(EA)/CNT. They even surpassed the activity of commercial Pt/C in terms of durability, Tafel slope, and MeOH tolerance.     

Precursor accumulation on nanocarbons for the synthesis of LaCoO3 nanoparticles as electrocatalysts for oxygen evolution reaction

Oxygen evolution reaction (OER) is a key step in energy storage devices. Lanthanum cobaltite (LaCoO₃) perovskite is an active catalyst for OER in alkaline solutions, and it is expected to be a low-cost alternative to the state-of-the-art catalysts (IrO₂ and RuO₂) because transition metals are abundant and inexpensive. For efficient catalysis with LaCoO₃, nanosized LaCoO₃ with a high surface area is desirable for increasing the number of catalytically active sites. In this study, we developed a novel synthetic route for LaCoO₃ nanoparticles by accumulating the precursor molecules over nanocarbons. This precursor accumulation (PA) method for LaCoO₃ nanoparticle synthesis is simple and involves the following steps: (1) a commercially available carbon powder is soaked in a solution of the nitrate salts of lanthanum and cobalt and (2) the sample is dried and calcined in air. The LaCoO₃ nanoparticles prepared by the PA method have a high specific surface area (12 m² g⁻¹), comparable to that of conventional LaCoO₃ nanoparticles. The morphology of the LaCoO₃ nanoparticles is affected by the nanocarbon type, and LaCoO₃ nanoparticles with diameters of less than 100 nm were obtained when carbon black (Ketjen black) was used as the support. Further, the sulfur impurities in nanocarbons significantly influence the formation of the perovskite structure. The prepared LaCoO₃ nanoparticles show excellent OER activity owing to their high surface area and perovskite structure. The Tafel slope of these LaCoO₃ nanoparticles is as low as that of the previously reported active LaCoO₃ catalyst. The results strongly suggest that the PA method provides nanosized LaCoO₃ without requiring the precise control of chemical reactions, harsh conditions, and/or special apparatus, indicating that it is promising for producing active OER catalysts at a large scale.

A simple synthetic process for LaCoO₃ nanoparticles based on the accumulation of precursors on nanocarbon supports was presented. The LaCoO₃ nanoparticles showed excellent OER activity owing to their high surface area and perovskite structure.     

Ferrocene anchored activated carbon as a versatile catalyst for the synthesis of 1,5-benzodiazepines via one-pot environmentally benign conditions

1,5-Benzodiazepine is considered as one of the central moieties in the core unit of most drug molecules. Construction of such moieties with a new C–N bond under solvent-free and mild reaction conditions is challenging. Herein, we present a benign protocol for one pot synthesis of 1,5-benzodiazepine derivatives by using ferrocene (FC) supported activated carbon (AC) as a heterogeneous catalyst. The catalyst FC/AC was characterized by several analytical and spectroscopic techniques to reveal its physicochemical properties and for structural confirmation. The synthesized catalyst FC/AC was explored for its catalytic activity in the synthesis of 1,5-benzodiazepines through condensation of o-phenylenediamine (OPDA) and ketones (aromatic and aliphatic) under solvent-free conditions. The robust 10 wt% FC/AC catalyst demonstrated appreciable activity with 99% conversion of diamines and 91% selectivity towards the synthesis of the desired benzodiazepine derivatives under solvent-free conditions at 90 °C in 8 h. Additionally, several reaction parameters such as catalyst loading, reaction temperature, effect of reaction time and effect of different solvents on selectivity were also studied and discussed in-depth. To understand the scope of the reaction, several symmetrical and unsymmetrical ketones along with different substituted diamines were tested with the synthesized catalyst. All prepared reaction products were obtained in good to efficient yields and were isolated and identified as 1,5-benzodiazepines and no side products were observed. The obtained catalyst characterization data and the activity studies suggested that, the synergetic effect occurred due to the uniform dispersion of ferrocene over the AC surface with numerous acidic sites which triggered the reaction of diamine and ketone to form the corresponding benzodiazepine derivative and the same was illustrated in the plausible mechanism. Furthermore, the synthesized catalyst was tested for leaching and recyclability, and the results confirmed that catalyst can be used for up to six consecutive cycles without much loss in the catalytic activity and its morphology which makes the process sustainable and economical for scale-up production. The present method offered several advantages such as an ecofriendly method, excellent yields, sustainable catalytic transformation, easy work-up and isolation of products, and quick recovery of catalyst.

1,5-Benzodiazepine is considered as one of the central moieties in the core unit of most drug molecules.     

Hierarchical Co(OH)2@NiMoS4 nanocomposite on carbon cloth as electrode for high-performance asymmetric supercapacitors

Hierarchical Co(OH)₂@NiMoS₄ nanocomposites were successfully prepared on a carbon cloth by using a simple two-step hydrothermal method coupled with a room-temperature vulcanization method. The resulting nanocomposites were composed of large-scale uniform Co(OH)₂ nanowires fully covered with ultrathin vertical NiMoS₄ nanoflakes. Because of the synergetic effect between Co(OH)₂ and NiMoS₄, the nanocomposites exhibited good electrochemical performance as a supercapacitor electrode. In particular, a specific capacity of 2229 F g⁻¹ was achieved at a current density of 1 A g⁻¹. In addition, an asymmetrical supercapacitor fabricated using activated carbon as the negative electrode and the as-synthesised nanocomposite as the positive electrode exhibited a maximum energy density of 59.5 W h kg⁻¹ at a power density of 1 kW h kg⁻¹ and excellent cycling stability (100% capacitance retention after 5000 cycles). These results indicate that the hierarchical Co(OH)₂@NiMoS₄ nanocomposite has great potential for practical application in high-performance energy storage devices.

A hierarchical Co(OH)₂@NiMoS₄ nanocomposite was prepared on the surface of carbon cloth, which exhibited good electrochemical performance as a supercapacitor electrode.     

Lignin-derived 3D porous graphene on carbon cloth for flexible supercapacitors

In this work, we reported a new method to fabricate flexible carbon-based supercapacitor electrodes derived from a commercialized and low-cost lignin. The fabrication process skips traditional stabilization/carbonization/activation for lignin-based carbon production. Also, the process reported here was green and facile, with minimum solvent use and no pretreatment required. Characterization of the lignin showed that it has common properties among all types of lignin. The lignin was impregnated on carbon cloth and then subjected to direct laser writing to form the desired electrodes (LLC). The results showed that lignin was successfully bonded to carbon cloth. The LLC has a good porous carbon structure with a high I_G/I_D ratio of 1.39, and a small interlayer spacing d₀₀₂ of 0.3436 nm, which are superior to most of the reported lignin-based carbons. Although not optimized, the fabricated LLC showed good supercapacitance behavior with an areal capacitance of 157.3 mF cm⁻² at 0.1 mA cm⁻². In addition, the superior flexibility of LLC makes it a promising electrode that can be used more widely in portable devices. Conceptually, this method can be generalized to all types of lignin and can define intriguing new research interests towards lignin applications.

Lignin was directly grown on carbon cloth via laser writing to form 3D porous graphene for flexible supercapacitors.     

In situ synthesis of nanostructured Fe3O4@TiO2 composite grown on activated carbon cloth as a binder-free electrode for high performance supercapacitors

Transition metal oxide (TMO) nanomaterials with regular morphology have received widening research attention as electrode materials due to their improved electrochemical characteristics. In this study we present the successful fabrication of an Fe₃O₄/TiO₂ nanocomposite grown on a carbon cloth (Fe₃O₄/TiO₂@C) used as a high-efficiency electrochemical supercapacitor electrode. Flexible electrodes are directly used for asymmetric supercapacitors without any binder. The increased specific surface area of the TiO₂ nanorod arrays provides sufficient adsorption sites for Fe₃O₄ nanoparticles. An asymmetric supercapacitor composed of Fe₃O₄/TiO₂@C is tested in 1 M Na₂SO₃ electrolyte, and the synergistic effects of fast reversible Faraday reaction on the Fe₃O₄/TiO₂ surface and the highly conductive network formed by TiO₂@C help the electrode to achieve a high areal capacitance of 304.1 mF cm⁻² at a current density of 1 mA cm⁻² and excellent cycling stability with 90.7% capacitance retention at 5 mA cm⁻² after 10 000 cycles. As a result, novel synthesis of a binder-free Fe₃O₄/TiO₂@C electrode provides a feasible approach for developing competitive candidates in supercapacitor applications.

Transition metal oxide (TMO) nanomaterials with regular morphology have received widening research attention as electrode materials due to their improved electrochemical characteristics.     

A doping-adsorption-pyrolysis strategy for constructing atomically dispersed cobalt sites anchored on a N-doped carbon framework as an efficient bifunctional electrocatalyst for hydrogen evolution and oxygen reduction

Renewable energy technology development focuses on the exploration of economical and efficient non-precious metal catalysts to replace precious metal catalysts in electrocatalytic reactions including oxygen reduction (ORR) and hydrogen evolution (HER). Herein, we synthesized a cobalt single atom catalyst anchored on a N-doped carbon framework by a doping-adsorption-pyrolysis strategy. The optimized Co SAs/CN-3 catalyst showed excellent HER and ORR bifunctional electrocatalytic performance, which could be attributed to the highly dispersed Co–N₄ active sites, large specific surface area and abundant pore structure. Density functional theory shows that the isolated active Co–N₄ site shows low hydrogen adsorption Gibbs free energy, and promotes the adsorption of H and oxygen-containing intermediates in HER and ORR. This work not only provides a new idea for the construction of transition metal catalysts with atomic accuracy but also provides powerful guidance for the development of efficient bifunctional electrocatalysts.

Atomically dispersed Co–N₄ sites anchored on a N-doped carbon framework catalyst were constructed by a novel doping-adsorption-pyrolysis strategy for bifunctional electrocatalytic HER and ORR.