Co(III) carboxamide complexes as electrocatalysts for water splitting

Water splitting is a promising approach for storing intermittent renewable energies, such as sunlight in the clean chemical bonds as a hydrogen fuel. Two water-soluble octahedral cobalt (III) complexes, [Co(bpb)(OAc)(H₂O)], 1, (bpb^2? = N,N′-bis[(2-pyridine carboxamide)-1,2-benzene] dianion) and [Co(cbpb)(OAc)(H₂O)], 2, (cbpb^2? = N,N′-bis[(2-pyridine carboxamide)-4-chloro-1,2-benzene] dianion) were synthesised and characterised by CHN elemental analysis, UV–Vis, FT-IR and single-crystal X-ray diffraction techniques. The two carboxamide ligands had been prepared in the ionic liquid TBAB as an environmentally benign reaction medium. The electrocatalytic water splitting activity of 1 and 2 showed that both complexes are highly active for the water splitting in aqueous solutions. Turn Over Frequency (TOF) values were, for 1 and 2 respectively, 527 and 490 mol of hydrogen in each mole of catalyst per hour at an overpotential of 738 mV (pH = 7.0). Such a performance can be ascribed to the flat ligands, the electroactivity of the metal centre and carboxamide ligands and the ability of losing the axial ligands around the metal-ion centre during the reduction process which provide different reduction pathways for an HER process.     

Electrocatalytic hydrogen evolution by Co(II) complexes of bistriazolylpyridines

Two cobalt complexes [Co(L₁)₂](ClO₄)₂⋅4CH₃CN (1) and [Co(L₂)₂](ClO₄)₂⋅2CH₃CN⋅0.5H₂O (2) of the new click-derived bistriazolylpyridines 2,6-bis(1-(pyridin-2-yl)-1H-1,2,3-triazol-4-yl)isonicotinate methyl ester (L₁) and 2,6-bis-(1-methoxycarbonylmethyl-1H-1,2,3-triazol-4-yl)isonicotinate methyl ester (L₂) were synthesized and characterized. The electrocatalytic hydrogen evolution reaction (HER) mediated by complexes 1 and 2 was studied in CH₃CN in the presence of acetic acid. Both complexes catalyzed HER with low overpotentials and high Faradaic efficiencies (370 mV and 93% for 1, 300 mV and 95% for 2). The distal substituents on the triazolyl moiety of the bistriazolylpyridines have apparent impacts on the redox and catalytic properties of 1 and 2. The catalytic behaviors were further studied using spectroelectrochemistry and the reductant cobaltocene. It was found that the reduction of the bistriazolylpyridines was necessary for the catalytic activity. Plausible pathways were proposed for the HER mediated by 1 and 2. This work provided some hints for the preparation of HER catalysts based on the redox-active triazolylpyridine ligands.     

Benzimidazole Schiff base copper(II) complexes as catalysts for environmental and energy applications: VOC oxidation,oxygen reduction and water splitting reactions

The new copper(II) complexes [Cu(μ-1κO:2κONN′-HL1)(μ-1κO:2κO′-NO₃)]₂.[Cu(μ-1κO:2κONN′-HL1)(CH₃OH)]₂(NO₃)₂ (1) and [Cu(κONN′-HL2)(μ-1κOO’:2κO′-NO₃)]_n (2), derived from the new pro-ligands H₂L1 = 2-(5,6-dihydroindolo[1,2-c]quinazolin-6-yl)-5-methylphenol and H₂L2 = 2-(5,6-dihydroindolo[1,2-c]quinazolin-6-yl)-4-nitrophenol, were synthesized and characterized by elemental analysis, FT-IR, ESI-MS, and their structural features were unveiled by single-crystal X-ray diffraction analysis. This discloses a dimeric structure for 1 and a polymeric infinite 1D metal-organic chain for 2. The complexes were evaluated as catalysts for the oxidation of toluene, a volatile organic compound (VOC), and for oxygen reduction and water splitting reactions. 1 exhibits a higher activity for the peroxidative conversion of toluene to oxygenated products (total yields up to 38%), whereas 2 demonstrates a superior performance for electrochemical energy conversion applications, i.e., for oxygen reduction (ORR), oxygen evolution (OER) and hydrogen evolution (HER) reactions in an alkaline medium in terms of higher ORR current densities, lower Tafel slope (73 mV dec^?1) and higher number of electrons exchanged (3.9), comparable to that of commercial Pt/C. Complex 2 also shows a better performance with lower onset potential and higher current densities for both OER and HER when studied as electrocatalyst for water splitting.     

Enhanced hydrogen storage capacity of NiAl-layered double hydroxide modified with Tb3Fe5O12 nanostructures

Under ultrasonic irradiation, the porous Tb₃Fe₅O₁₂ (TFO) and Nickel Aluminum layer double hydroxide (NiAl-LDH) were synthesized by investigation the effect of sonication time. Synthesis of TFO was conducted in the presence of tetradentate Schiff-base ligand H₂salophen, [N,N′-bis(salicylidene)-1,2-phenylenediamine] as complexing agent to size controlling and further growth prevention of crystals. The resultant nanocomposites of TFO/NiAl-LDH used as novel active compounds for applying in hydrogen storage strategies. Comprehensively, the hydrogen capacitance after 15 cycles was displayed on the pure NiAl-LDH and TFO materials about 115 and 334 mAhg⁻¹ respectively. It demanded the maximum capacitance for Tb₃Fe₅O₁₂/NiAl-LDH nanocomposites was 451 mAhg⁻¹, which was higher than the initial NiAl-LDH structure. It was exposed from the spillover effect that; the endorsed electrochemical hydrogen storage (EHS) performance is ascribed to the reaction of the redox pair of Fe³⁺/Fe²⁺ at the active sites throughout the EHS procedure. This work delivers a novel plan and potential sorption electrode materials to progress the intrinsic action of layered compounds.     

Cobalt phosphide nanoparticles embedded in 3D N-doped porous carbon for efficient hydrogen and oxygen evolution reactions

An electrocatalyst based on a unique three-dimensional (3D) N-doped porous carbon sheet networks embedded with CoP₂ nanoparticles (CoP₂@3D-NPC) was synthesized by a facile pyrolysis process as well as an in-situ phosphatization method. The improved CoP₂@3D-NPC hybrid materials show excellent electrocatalytic activity toward HER and OER. This material provides a low overpotential of 126 mV at 10 mA cm⁻² in 0.5 M H₂SO₄ and 167 mV at 20 mA cm⁻² in 1.0 M KOH for HER with a small Tafel slope value of 59 mV dec⁻¹, respectively. Besides, it is also active for the OER under alkaline conditions. Such a prominent property of the CoP₂@3D-NPC electrocatalyst could be attributed to its excellent electrical conductivity of 3D carbon substrate, strong synergistic effect between CoP₂ nanoparticles and carbon nanosheet as well as extra active sites created by the N-doped structure.     

Aromatic amines as proton carriers for catalytic enhancement of hydrogen evolution reaction on copper in acid solutions

The catalytic effect of some aromatic amines towards hydrogen evolution reaction on copper in diluted sulfuric acid solution has been studied. Since amines facilitate the transport of protons from the solution bulk to the interface in the cathodic hydrogen evolution reaction, they are known as proton carriers. The catalytic effect of aniline, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N,N-diethylaniline, o-toluidine, m-toluidine and p-toluidine has been highlighted by linear sweep voltammetry. The kinetic parameters for the hydrogen evolution reaction (cathodic transfer coefficient 1-α and exchange current density i_o) in the presence of the studied aromatic amines were derived from the Tafel plots. It has been found that the catalytic effect of amines is active even at low concentration. Thus, in 0.5 mol L⁻¹ H₂SO₄ solution the exchange current density increases by two orders of magnitude, from 2.01⋅10⁻⁵ A m⁻² in the absence of aniline to 2.85⋅10⁻³ A m⁻² in the presence of 10⁻⁴ mol L⁻¹ aniline. The influence of amines concentration on the catalytic effect is described in detail for the case of m-toluidine. The results obtained by voltammetry have been compared with electrochemical impedance spectroscopy data. Furthermore, the kinetic parameters for the hydrogen evolution reaction have been determined as a function of temperature and amines concentration.     

Efficient electrocatalytic and photocatalytic hydrogen evolution using a linear trimeric thiolato complex of nickel

Increasing interest has been paid to the development of earth-abundant metal complexes as promising surrogates of noble-metal platinum and biological catalysts hydrogenases for catalyzing the hydrogen evolution reaction. In this study, we report on a molecular H₂-evolving catalyst based on a linear trimeric thiolato complex of nickel Ni₃(L^N2S2)₂ (L^N2S2 = N,N′-dimethyl-N-N′-bis(2-mecaptoethyl)-ethylenediaminato). Electrochemical studies showed that the trinuclear nickel complex Ni₃(L^N2S2)₂ can electrocatalyze hydrogen evolution from weakly acidic solutions with remarkable turnover frequencies (3495 s^?1 at ?1.98 V and 715 s^?1 at ?1.58 V vs SCE). An efficient noble-metal-free homogeneous photocatalytic system for hydrogen generation from water working under visible light irradiation was further constructed by using the target nickel complex as photocatalyst, fluorescein (Fl) as photosensitizer (PS), and triethylamine (TEA) as sacrificial electron donor. Our studies showed that Ni₃(L^N2S2)₂ can be used in purely aqueous solution and gave a turnover number (TON, vs catalyst) for H₂ evolution of 790, corresponding to a TOF 60 h^?1. The results show that multinuclear nickel(II) complexes are a promising new direction for molecular catalysts for the electro- and photoreduction of protons.     

Facile synthesis of Co3O4 nanoparticles from a novel tetranuclear cobalt(III) complex. Application as efficient electrocatalyst for oxygen evolution reaction in alkaline media

A tetranuclear cobalt complex [Co₄^III(L′)₆] was synthesized by the direct reaction of cobalt(II) acetate with a N₂S₂ Schiff base ligand H₂L containing a disulfide bond under aerobic conditions {H₂L = 2,2′-bis(2-hydroxynaphthyliminobenzyl)disulfide}. The X-ray crystal structure of [Co₄^III(L′)₆] indicates reductive disulfide bond scission of H₂L upon reaction with Co²⁺ to give [L^′]^2–. Furthermore, cobalt oxide nanoparticles of about 30 nm size were synthesized by thermal decomposition of [Co₄^III(L′)₆] as a precursor. The Co₃O₄ nanoparticles were characterized by XRD, FE-SEM, TEM, and FT-IR spectroscopy. The electrocatalytic activity of the resulting oxide was examined in oxygen evolution reaction (OER) by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) in 1.0 mol L^?1 KOH. The NPs displays efficient electrocatalytic activity for oxygen evolution reaction with a current density of 10.0 mA cm^?2 at 1.65 V, good onset potential of 1.52 V vs. RHE and small Tafel slope of 44 mV dec^?1.     

Tuning the microstructure of organosilica membranes with improved gas permselectivity via the co-polymerization of 1,2-bis(triethoxysilyl)ethane and 1,2-bis(triethoxysilyl)methane

1,2-bis(triethoxysilyl)ethane (BTESE)-derived membranes have proven thermal and hydrothermal stability and molecular sieving properties. However, BTESE-derived membranes still have low gas permselectivity due to their loose structure. Herein, we propose a novel strategy of co-polymerization using precursors of both BTESE and 1,2-bis(triethoxysilyl)methane (BTESM) to improve the gas permselectivity of BTESE-derived membranes. BTESM is introduced into BTESE network and the microstructure can be adjusted by different molar ratios of BTESE to BTESM. We find that, as the content of BTESM increase, H₂ permeations of BTESE-BTESM membranes remain nearly constant, while the permeations of larger gases (CO₂ and N₂ etc.) exhibit a greatly decreased. The membrane with a molar ratio of BTESE:BTESM = 3:7 exhibits the highest H₂/CO₂ (11.3) and H₂/N₂ (26.8) permselectivity while having a relatively high H₂ permeance (1.52 × 10^?6 mol m² s^?1?Pa^?1). Our findings may provide novel insights into preparation of co-polymerization organosilica membranes with excellent H₂/CO₂ and H₂/N₂ separation performance.     

A high active hydrogen evolution reaction electrocatalyst from ionic liquids-originated cobalt phosphide/carbon nanotubes

Ionic liquid/carbon nanotubes (IL/CNTs) composite was applied as the precursor to prepare CNTs-supported cobalt phosphide via low-temperature phosphidation. CoP_(MBMG)/CNTs, generated from N,N-bis(4-(methoxycarbonyl)benzyl)-N-methyl-d-glucaminium dibromodichlorocobaltate(II) (MBMG)₂-CoCl₂Br₂), exhibits the best catalytic activity toward hydrogen evolution reaction with an onset overpotential of 55 mV, a Tafel slope of 58 mV dec^?1, 95% Faradaic efficiency (FE), current densities of 10 and 20 mA cm^?2 at overpotentials of 135 and 160 mV, and it can maintain the catalytic activity for at least 27 h. FT-IR, Raman spectroscopy, XPS and XRD were utilized to investigate the phosphidation process. All experimental results confirmed that anion from (MBMG)₂-CoCl₂Br₂ can form CoP and glucaminium-based cation can become amorphous carbon after phosphidation to obtain the high HER activity of CoP_(MBMG)/CNTs.     

Ultrasmall Mo2C in N-doped carbon material from bimetallic ZnMo-MOF for efficient hydrogen evolution

The exploration and development of cost-effective and highly stable electrocatalysts with the highest possible energy efficiency remain a constant pursuit in the catalyst design and synthesis for electrocatalytic hydrogen evolution reaction (HER). In this work, a convenient approach is proposed to synthesize a type of ultrafine Mo₂C nanoparticles in average sizes of 3–4 nm embedded in hierarchically porous N-doped carbon material calcined from bimetallic ZnMo-MI (MI = 2-methylimidazole) is obtained at 1000 °C, denoted as ZnMo-MI-1000. First of all, the crystalline hybrid metal-organic framework of ZnMo-MI is fabricated from zeolitic imidazolate framework of Zn-MI precursors via solvothermal reaction, in which the conversion from Zn-MI to ZnMo-MI occurs gradually over time. After calcination, the as-obtained ZnMo-MI-1000 sample shows a satisfying HER performance with the small overpotential of 83.0 mV in 0.5 M H₂SO₄ and 100.1 mV in 1.0 M KOH to reach a current density of 10 mA cm^?2, which is attributed to ultrasmall Mo₂C, Mo and N-doped graphitic carbon matrix. The multiporous network of ZnMo-MI-1000 can provide continuous mass transportation with a minimal diffusion resistance that produce effective electrocatalytic kinetics in both acidic and alkaline media, which is utilized as a highly active and durable nonprecious metal electrocatalyst for HER.     

N,N-bis(sulfopropyl)aminyl-4-phenyl polysulfone and O,O′-bis(sulfopropyl)resorcinol-5-yl-4-phenyl polysulfone composite membrane for proton exchange membrane fuel cells

Novel functionalized polysulfone with high local density of sulfonic acid groups, N,N-bis(sulfopropyl)aminyl-4-phenyl polysulfone or O,O′-bis(sulfopropyl)resorcinol-5-yl-4-phenyl polysulfone (PSF-X-C₃H₆SO₃H, X = N or O) are synthesized. These polymers are synthesized by bromination of polysulfone followed by Suzuki cross-coupling reaction to graft the aminophenyl groups and the dimethoxyphenyl groups onto the polymeric backbone, followed by introduction of the sulfopropyl groups via sultone ring-opening reaction. In addition, the composite membrane of PSF-O-C₃H₆SO₃H and PSF-N-C₃H₆SO₃H is also synthesized for comparison. The maximum proton conductivity of composite PSF-O-C₃H₆SO₃H and PSF-N-C₃H₆SO₃H reaches 46.66 mS cm⁻¹ at 95 °C and 90% RH, higher than PSF-O-C₃H₆SO₃H (42.06 mS cm⁻¹) and PSF-N-C₃H₆SO₃H (38.76 mS cm⁻¹). Meanwhile, the composite exhibits compromised water uptake and swelling ratio, and low methanol permeability. The excellent overall performance of the composite is attributed to phase-separation between the hydrophilic and the hydrophobic subphases, and the hydrogen-bonding network developed in the hydrophilic subphases.     

Electrocatalytic hydrogen evolution of a cobalt A2B triaryl corrole complex containing –N=PPh3 group

A new cobalt 5,15-bis(perfluorophenyl)-10-(4-N-(triphenylphosphoranylidene)-2,3,5,6-tetrafluorophenyl) corrole complex (Co-BPNC-PPh₃) containing –N=PPh₃ group has been prepared by Staudinger reaction and characterized by the single-crystal X-ray structure determination. The electrocatalytic hydrogen evolution reaction (HER) of Co-BPNC-PPh₃ by using acetic acid (AcOH), trifluoroacetic acid (TFA) and p-toluenesulfonic acid (TsOH) as proton sources in N, N-dimethylformamide (DMF) solvent had been investigated. The turn-over frequency (TOF) value of Co-BPNC-PPh₃ was observed 450 h^?1 at an overpotential of 838 mV in neutral aqueous solution, showing excellent electrocatalytic HER activity. This Co-BPNC-PPh₃ exhibited excellent durability and stability in the 5-hours electrolysis. Its activity is also better than cobalt 5, 10, 15-(tris-pentatfulorophenyl) corrole (Co-TPFC-PPh₃), which may be ascribed to the –N=PPh₃ proton relay effect in the electrocatalytic HER.     

Vapor-assisted engineering heterostructure of 1D Mo3N2 nanorod decorated with nitrogen-doped carbon for rapid pH-Universal hydrogen evolution reaction

Reasonable construction of heterostructure is of significance yet a great challenge towards efficient pH-universal catalysts for hydrogen evolution reaction (HER). Herein, a facial strategy coupling gas-phase nitridation with simultaneous heterogenization has been developed to synthesize heterostructure of one-dimensional (1D) Mo₃N₂ nanorod decorated with ultrathin nitrogen-doped carbon layer (Mo₃N₂@NC NR). Thereinto, the collaborative interface of Mo₃N₂ and NC is conducive to accomplish rapid electron transfer for reaction kinetics and weaken the Mo–H_ads bond for boosting the intrinsic activity of catalysts. As expected, Mo₃N₂@NC NR delivers an excellent catalytic activity for HER with low overpotentials of 85, 129, and 162 mV to achieve a current density of 10 mA cm^?2 in alkaline, acidic, and neutral electrolytes, respectively, and favorable long-term stability over a broad pH range. As for practical application in electrocatalytic water splitting (EWS) under alkaline, Mo₃N₂@NC NR || NiFe-LDH-based EWS also exhibits a low cell voltage of 1.55 V and favorable durability at a current density of 10 mA cm^?2, even surpassing the Pt/C || RuO₂-based EWS (1.60 V). Consequently, the proposed suitable methodology here may accelerate the development of Mo-based electrocatalysts in pH-universal non-noble metal materials for energy conversion.     

Cobaltous selenide/g-C3N4 heterojunction photocatalyst based on double-electron migration mechanism promotes hydrogen production and tetracycline hydrochloride degradation

Regulating photogenerated charge carrier transfer kinetics in multi-component heterostructure by surface-interface design is of great significance for accelerating efficiently photocatalytic hydrogen evolution reaction. Herein, a novel binary CoSe₂/CN_NS composite is successfully fabricated by a successive high-temperature calcination method of g-C₃N₄ followed by in-situ hot injection process of CoSe₂ for the first time. The optimal 7.5% CoSe₂/CN_NS heterostructure reaches moderate hydrogen production rate of 1386.8 μmol·g^?1·h^?1 and exhibits good mineralization efficiency for tetracycline hydrochloride (40.6%) within 120 min under light irradiation, respectively. The photogenerated charge migration behaviors, the generation process and function of various radical species (H₂O₂, ·OH and ·O₂^?) are detailedly analyzed. Moreover, photocatalytic hydrogen evolution reaction process and the intermediates and active species for tetracycline hydrochloride degradation can also be discussed. Such significantly enhanced photocatalytic activity can be resulting from good light trapping ability, rapid photocarriers transfer efficiency and accelerated H₂O₂ decomposition ability via a continuous two-electron/two-step reduction route. This work provides an effective strategy to control and understand the charge migration kinetics as well as to suppress H₂O₂ production during photocatalytic hydrogen evolution process.     

A molecular Keggin polyoxometalate catalyst with high efficiency for visible-light driven hydrogen evolution

A molecular Keggin polyoxometalate catalyst K₇[Co^IIICo^II(H₂O)W₁₁O₃₉](1) was successfully synthesized and efficiently catalyzed the hydrogen evolution. To the best of our knowledge, the molecular Keggin polyoxometalate catalyst 1 is the first reported polyoxometalate containing cobalt with efficient hydrogen production activity under the visible light irradiation. Under the optimal photocatalytic condition (photoirradiation at λ ≥ 420 nm, Eosin-Y as the photosensitizer, triethanolamine as the electron donor and Pt produced in situ photoreduction as co-catalyst), the turnover number (TON/based on catalyst) reached as high as 100; the initial quantum yield and the initial turnover frequency (TOF) at the first 10 min were 29% and 0.025 s⁻¹, respectively. The hydrogen evolution average rate of 1 achieved 13,395 μmol h⁻¹ g⁻¹, as far as we are concerned, which is the highest among all the polyoxometalates photocatalytic systems reported so far. A possible mechanism of the hydrogen evolution reaction was proposed on the basis of steady-state fluorescence decay studies.     

Synthesis,structural characterization and thermal decomposition studies of (N2H5)2B12H12 and its solvates

A series of salts of the B₁₂H₁₂²⁻ anion has been prepared: a solvent-free (N₂H₅)₂B₁₂H₁₂, its solvates – (N₂H₅)₂B₁₂H₁₂·H₂O, (N₂H₅)₂B₁₂H₁₂·2(CH₃CN), (N₂H₅)₂B₁₂H₁₂·(CH₃OH), and the salt of a protonated azine – [(CH₃)₂CNNHC(CH₃)₂]₂B₁₂H₁₂. These compounds have been synthesized from the commercially available precursors via one- or two-step procedures and fully identified on the basis of single-crystal and powder X-ray diffraction. At room temperature (N₂H₅)₂B₁₂H₁₂ crystallizes in C2/c space group, with a = 18.480(5) Å, b = 6.5344(19) Å, c = 13.106(4) Å and β = 131.911(16)^o, V = 1177.8(7) ų, Z = 4. While this compound nominally contains ca. 10.7 wt% of hydrogen, it thermally decomposes above 200 °C releasing mainly N₂ and NH₃, with H₂ being only the minor gaseous product. Contrary to the recently reported case of hydrazinates of borohydrides, doping with 5 mol% of FeCl₃ does not increase the relative amount of hydrogen significantly, however, it alters the ratio of N₂ and NH₃.     

Monometallic,bimetallic, and trimetallic chalcogenide-based electrodes for electrocatalytic hydrogen evolution reaction

Cu₂CoSnS₄, Cu₂SnS₃, Cu₂CoS₄, Co₂SnS₃, Cu₂S, CoS₂, and SnS₂ were synthesized using a one-step solvent-free solid-phase approach. The surface structure, morphology, and composition were characterized using an X-ray diffractometer (XRD), Fourier-Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-ray Photoelectron Spectroscopy (XPS). The characterizations reveal pure phase formation and porous morphology. Further, the Hydrogen evolution reaction was performed using Cu₂CoSnS₄, Cu₂SnS₃, Cu₂CoS₄, Co₂SnS₃, Cu₂S, CoS₂, and SnS₂-based electrodes. Amid all electrocatalysts, Cu₂CoSnS₄ shows an excellent hydrogen evolution reaction with a low overpotential of ?192.1 mV at ?10 mA/cm² in 0.5 M H₂SO₄. And higher current density. Cu₂CoSnS₄ also shows a lower Tafel slope of 98.6 mV/dec and charge transfer resistance than mono and bimetallic chalcogenide-based electrodes. The Cu₂CoSnS₄ exhibit very good stability for ～22 h at ?10 mA/cm² current density in 0.5 M H₂SO₄.     

Studies on electrochemical properties of thionyl chloride reduction by Schiff base metal(II) complexes

Electrocatalytic effects associated with the reduction of thionyl chloride in a LiAlCl₄–SOCl₂ electrolyte solution containing Schiff base metal(II) (metal (M): Co, Ni, Cu and Mn) complexes are evaluated by determining the kinetic parameters for the reactions using cyclic voltammetry at a glassy carbon electrode. The charge-transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. Catalytic effects are demonstrated from both a shift in the reduction potential for the thionyl chloride in a more positive direction and an increase in peak currents. The reduction of thionyl chloride is diffusion controlled. Catalytic effects are larger for thionyl chloride solutions containing M(II)(1,5-bis(salicylidene imino) pentane) (M(II)(SALPE)) rather than M(II)(1,3-bis(salicylidene imino) propane) (M(II)(SALPR)). Significant improvements in cell performance are found in terms of the both thermodynamics and kinetic parameters for the thionyl chloride reduction. An exchange rate constant, k⁰, of 1.89×10⁻⁸ cm s⁻¹ is found at the bare electrode, while larger values of 2.79×10⁻⁸ to 2.09×10⁻⁶ cm s⁻¹ are observed in the case of the catalyst-supported glassy carbon electrode.     

Fabrication of P-doped Co9S8/g-C3N4 heterojunction for excellent photocatalytic hydrogen evolution

Developing lower-cost and higher-efficient photocatalysts is still a major challenge for the solar to hydrogen energy conversion by photocatalytic water splitting. Herein, P-doped Co₉S₈ (P–Co₉S₈) was synthesized by a hydrothermal process using low-cost RP as raw material, and then P–Co₉S₈ was employed to construct heterojunction with g-C₃N₄ via a mechanical-mixing method. Investigation shows that P–Co₉S₈ can not only improve the electrical conductivity and surface area of the composite, but also can lower the over-potential of H₂ evolution, leading to an enhanced H₂ evolution kinetics. The H₂ evolution rate of resultant 25% P–Co₉S₈/g-C₃N₄ reached 4362 μmol g⁻¹ h⁻¹ under UV and visible light, being nearly 121.2 times higher than that of g-C₃N₄. The charge transfer between P–Co₉S₈ and g-C₃N₄ follows the Type-I route based on the photoelectrochemical analysis, leading to more electrons on the conduction band of P–Co₉S₈ to participate the H₂ evolution processes. This work provides a new way for preparation of P-doped sulfides with potential applications in the field of photocatalysis.