Electrocatalytic Activity For Reduction Research Articles

Hybrid Nanoparticles: Ni and Au Decorated with [FeFe]‐Hydrogenase Mimics

Complexes [(μ‐S₂C₂H₄NHR)Fe₂(CO)₆] (R = p‐C₆H₄‐OCO(CH₂)₉Br (3a); R = p‐C₆H₄‐OCO(CH₂)₈CH₃ (3b)) were used as stabilizing agents in the synthesis of Ni@3 and Au@3 nanoparticles (NPs), which are the first reported stable metallic NPs decorated with [(μ‐S₂C₂H₄NHR)Fe₂(CO)₆] moieties. Electrochemical analysis reveals that incorporating the hydrogenase mimic into the NPs lowers the overpotential and enhances proton reduction electrocatalytic activity in organic media. The NPs act similarly to the [Fe₄S₄] cluster in natural enzymes, functioning as an electron reservoir/relay.

Enhanced Electrocatalytic Activity for Nitrate Reduction to Ammonia by Tuning a Ruthenium Oxidation State of Ruthenium-Based Nanotubes

Enhanced Electrocatalytic Activity for Nitrate Reduction to Ammonia by Tuning a Ruthenium Oxidation State of Ruthenium-Based Nanotubes

Mechanistic Aspects of Selenate Reduction on CU(UPD) on AU Electrodes

Recent findings in our laboratories have shown that copper1and cadmium2 underpotential deposited on polycrystalline Au electrodes, can mediate the reduction of in 0.1 M HClO4 aqueous solutions, to yield irreversibly adsorbed elemental Se allowing its detection down to the nM range. Current efforts are focused on gaining a better understanding of the the factors that govern this unique electrocatalytic phenomenon by employing a combination of electrochemical, microgravimetric, and optical techniques, using Cu as the UPD species. Correlations have been sought between the rates of this process and the coverage of Cu(UPD), the concentration of and, to a more limited extent, the applied potential in 0.1 M HClO4 solutions. Experimental conditions were selected to unveil the functional dependence of the kinetics on each of the aforementioned factors, while keeping the others constant, in solutions both quiescent and in the presence of convective flow. A number of interesting observations were made based on the data collected. In particular, shown in Panel C, Fig. 1, are plots of the charge associated with the oxidation of adsorbed Cu and Se, QCu and QSe, respectively (see Panel C), obtained from the area under the peaks shaded in light blue and yellow in Panels A and B, Fig, 1, respectively, vs (see below). These data were recorded during linear potential scans following polarization of the electrode at Ehold = 0.325 V for various times, thold (see Panels A-C, Fig. 1), where the linear character of the data in solutions is consistent with Cu(UPD) proceeding under strict diffusion control. As indicated by the QSe data, the electrode displayed electrocatalytic activity for reduction only for QCu > ca. 80 μC cm2-. Additional insight was obtained from measurements of the electrode weight as a function of using a quartz crystal microbalance (see Panel D, Fig.1), which yielded evidence for adsorption only for QCu > ca. 80 μC cm2-, pointing to the formation of a surface-bound adduct, as a necessary step for reduction to ensue. On this basis, we propose that for QCu > ca. 80 μC cm2 the mechanism for reduction involves, as a first step, the reversible formation of the adduct, Eq. (1) followed by its irreversible reduction, generating adsorbed elemental Se, Cu|Se(ads), Eq. (2).Atomically resolved images of Cu(UPD) on Au(111) obtained with a scanning tunneling microscope for the closely related sulfate ion, strongly suggest that the active site involved adsorption on the empty Au sites of the so-called √3´x√3 superstructure (see Insert in Panel A, Fig. 1). A similar conclusion was drawn based on measurements performed with rotating Cu ring-polycrystalline Au disk electrodes, RRDE, at constant Cu(UPD) coverage and applied potential for various solution compositions. Quantitative analyses of all the data, which included numerical simulations, yielded kf/kr, and kET values in the range (2.4 – 3.23) ´ 106 cm3 mol-1 and (2.5 – 9) ´ 10-3 s-1, respectively. Acknowledgments Support for this work was provided by NSF CHEM 1808592

Electrocatalytically active and charged natural chalcopyrite for nitrate-contaminated wastewater purification extended to energy storage Zn-NO3− battery

Charged natural chalcopyrite (CuFeS2, Ncpy) was developed for a three-dimensional electrochemical nitrate reduction (3D ENO3−RR) system with carbon fiber cloth cathode and Ti/IrO2 anode and Zn-NO3− battery. The 3D ENO3−RR system with Ncpy particle electrodes (PEs) possessed superior nitrate removal of 95.6 % and N2 selectivity of 76 % with excellent reusability under a broad pH range of 2–13 involving heterogeneous and homogeneous radical mechanisms. The Zn-NO3− battery with Ncpy cathode delivered an open-circuit voltage of 1.03 V and a cycling stability over 210 h. It was found that Ncpy PEs functioned through self-oxidation, surface dynamic reconstruction (Cu1.02Fe1.0S1.72O1.66 to Cu0.61Fe1.0S0.27O2.98), intrinsic micro-electric field (CuI, S2− anodic and FeIII cathodic poles), and reactive species (•OH, SO4•−, 1O2, •O2− and •H) generation. Computational analyses reveal that CuFeS2(112) surface with the lowest surface energy preferentially exposes Fe and Cu atoms. Cu site is beneficial for reducing NO3− to NO2−, Fe and Fe−Cu dual sites are conducive to N2 selectivity, lowering the overall reaction barriers. It paves the way for selective NO3− reduction in wastewater treatment and can be further extended to energy storage devices by utilizing low-cost Ncpy.

Lithium cation-doped tungsten oxide as a bidirectional nanocatalyst for lithium-sulfur batteries with high areal capacity

Lithium-sulfur (Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide (Li2S) oxidation barrier, especially under high sulfur loadings. Here, we report a Li cation-doped tungsten oxide (LixWOx) electrocatalyst that efficiently accelerates the S↔Li2S interconversion kinetics. The incorporation of Li dopants into WOx cationic vacancies enables bidirectional electrocatalytic activity for both polysulfide reduction and Li2S oxidation, along with enhanced Li+ diffusion. In conjunction with theoretical calculations, it is discovered that the improved electrocatalytic activity originates from the Li dopant-induced geometric and electronic structural optimization of the LixWOx, which promotes the anchoring of sulfur species at favourable adsorption sites while facilitating the charge transfer kinetics. Consequently, Li-S cells with the LixWOx bidirectional electrocatalyst show stable cycling performance and high sulfur utilization under high sulfur loadings. Our approach provides insights into cation engineering as an effective electrocatalyst design strategy for advancing high-performance Li-S batteries.

Effect of nickel and selenium co-doping on molybdenum disulfide structure and its electrochemical activity in polysulfide electrolyte

The development of a low-cost, and highly effective platinum (Pt)-free counter electrode (CE) that is highly stable towards polysulfide electrolyte presents a substantial challenge. Trigonal Molybdenum disulfide (1T-MoS2) has shown good chemical stability toward polysulfide electrolytes. In this study, 1T-MoS2 was prepared by co-doping with nickel (Ni) and selenium (Se) into MoS2 through hydrothermal method and utilizing its reduction activity toward polysulfide electrolyte. According to electrochemical impedance spectroscopy (EIS) analysis, Ni-Se-MoS2 has a low charge transfer resistance and electron recombination lifetime. In addition, cyclic voltmeter (CV) analysis reveals a high absolute area indicating a high level of electrocatalytic activity for polysulfide reduction at the electrolyte/counter electrode (CE) interface. The XRD analysis shows that the phase shifting of 2H MoS2 to 1 T MoS2 and the intensity of the co-doped sample is lower than that of others. SEM analysis reveals a microsphere-flower-like morphology that increases specific surface area.

Thermal-driven Dispersion of Bismuth Nanoparticles among Carbon Matrix for Efficient Carbon Dioxide Reduction.

The poor electrocatalytic stability and rapid deactivation of metal electrocatalysts are always present in the electrocatalytic conversion of carbon dioxide (CO2) due to the harsh reduction condition. Herein, we demonstrate the controllable dispersion of ultrafine bismuth nanoparticles among the hollow carbon shell (Bi@C-700-4) simply by a thermal-driven diffusion process. The confinement effect of nitrogen-doped carbon matrix is able to low the surface energy of bismuth nanoparticles against the easy aggregation commonly observed for the thermal treatment. On the basis of the synergistic effect and confinement effect between bismuth nanoparticles and carbon matrix, the highly dispersed active sites render the obviously improved electrocatalytic activity and stability for carbon dioxide reduction into formate. The in-situ experimental observation on the reduction process and theoretical calculations reveal that the incorporation of bismuth nanoparticles with nitrogen-doped carbon matrix would promote the activation of CO2 and the easy formation of key intermediate (*OCHO), thus leading the enhanced electrocatalytic activity, with a Faradaic Efficiency (FE) of formate about 94.8% and the long-time stability. Furthermore, the coupling of an anode for 5-hydroxymethylfurfural oxidation reaction (HMFOR) in solar-driven system renders the high 2,5-furandicarboxylic acid (FDCA) yield of 81.2%, presenting the impressive solar-to-fuel conversion.

Highly improved ionic conduction in reverse spinel structured CoAl2O4 and ZnO heterostructure through interfacial disordering

For ceramic fuel cells with low temperatures operation (LT-CFCs; 350°-550 °C), increasing the ionic conductivity and improving the oxygen reduction electrocatalytic activity response at low operating temperatures would be highly desired. This Study presents a novel semiconductor heterostructure composite with a competent electrolyte membrane for LT-CFCs. The composite comprises CoAl2O4 (CA) in a spine-like structure and wurtzite-structured ZnO. We have demonstrated a button-sized CFC under H2 and ambient air environment delivering a high power density of 835 mW-cm−2 at 550 °C, with potential operating up-to 400 °C. Compared to ZnO and CA alone, the CA-ZnO heterostructure composite has reduced oxygen vacancy production and activation energy, facilitating ion transport more quickly through the CA-Zn interface. Density functional theory (DFT) computations, photoelectron spectroscopy, U-visible, X-ray diffraction, and HR-TEM are the characterization techniques used to study the enhanced ionic conduction of the CA-ZnO heterostructure composite. These results imply that the heterostructure approach works better than the simple bulk structure for the electrolyte application of LT-SOFCs.

Theoretical calculations and experimental verification of carbon dioxide reduction electrocatalyzed by metalloporphyrin

Metal-functionalized porphyrin-like graphene structures are promising electrocatalysts for carbon dioxide reduction reaction (CO2RR) as their metal centers can modulate activity. Yet, the role of metal center of metalloporphyrins (MTPPs) in CO2 reaction activity is still lacking deep understanding. Here, CO2RR mechanism on MTPPs with five different metal centers (M = Fe, Co, Cu, Zn and Ni) are examined by first-principles calculations. The *COOH formation is the rate determined step on the five MTPP structures, and the CoTPP exhibits the best CO2RR activity while ZnTPP and NiTPP are the worst, which is also verified by our experiment. The CO2RR activity is controlled by adsorption states of intermediates (*CO, *COOH), i.e., chemisorption (e.g., on CoTPP) and physisorption (on ZnTPP and NiTPP) of intermediates will lead to good and poor activity, respectively. The deeper the d-band center of the porphyrin ring complexed metal atom, the weaker bonding of MTPP with CO and COOH. Theoretical calculations and experimental results indicate that MTPPs with Co and Fe centers lead to a reduction in the energy barriers for the two uphill reaction steps in the electrocatalytic CO2 reduction process, thereby enhancing CO2 reduction electrocatalytic activity. Faradaic efficiency of CO is correlated with the reaction energy barrier of the first proton-coupled electron reduction process, displaying a strong linear correlation. This work provides a fundamental understanding of MTPPs used as electrocatalysts for CO2RR.

Advancing electrochemical nitrogen reduction: Efficacy of two-dimensional SiP layered structures with single-atom transition metal catalysts

Researchers are interested in single-atom catalysts with atomically scattered metals relishing the enhanced electrocatalytic activity for nitrogen reduction and 100 % metal atom utilization. In this paper, we investigated 18 transition metals (TM) spanning 3d to 5d series as efficient nitrogen reduction reaction (NRR) catalysts on defective 2D SiPV layered structures through first-principles calculation. A systematic screening identified Mo@SiPV, Nb@SiPV, Ta@SiPV and W@SiPV as superior, demonstrating enhanced ammonia synthesis with significantly lower limiting potentials (−0.25, −0.45, −0.49 and −0.15 V, respectively), compared to the benchmark −0.87 eV for the defective SiP. In addition, the descriptor ΔG*N was introduced to establish the relationship between the different NRR intermediates, and the volcano plot of the limiting potentials were determined for their potential-determining steps (PDS). Remarkably, the limiting voltage of the NRR possesses a good linear relationship with the active center TM atom Ɛd, which is a reliable descriptor for predicting the limiting voltage. Furthermore, we verified the stability (using Ab Initio Molecular Dynamics − AIMD) and high selectivity (UL(NRR)-UL(HER) > -0.5 V) of these four catalysts in vacuum and solvent environments. This study systematically demonstrates the strong catalytic potential of 2D TM@SiPV(TM = Mo, Nb, Ta, W) single-atom catalysts for nitrogen reduction electrocatalysis.

Red Carbon Mediated Formation of Cu2O Clusters Dispersed on the Oxocarbon Framework by Fehling's Route and their Use for the Nitrate Electroreduction in Acidic Conditions.

The oligomers of carbon suboxide, known as red carbon, exhibit a highly conjugated structure and semiconducting properties. Upon mild heat treatment, it transforms into a carbonaceous framework rich in oxygen surface terminations, called oxocarbon. In this study, the abundant oxygen functionalities are harnessed as anchors to create oxocarbon-supported nanohybrid electrocatalysts. Starting with single atomic Cu (II) strongly coordinated to oxygen atoms on red carbon, the Fehling reaction leads to the formation of Cu2O clusters. Simultaneously, a covalent oxocarbon framework emerges via cross-linking, providing robust support for Cu2O clusters. Notably, the oxocarbon support effectively stabilizes Cu2O clusters of very small size, ensuring their high durability in acidic conditions and the presence of ammonia. The synthesized material exhibits a superior electrocatalytic activity for nitrate reduction under acidic electrolyte conditions, with a high yield rate of ammonium (NH4 +) at 3.31mmolh-1mgcat -1 and a Faradaic efficiency of 92.5% at a potential of -0.4V (vs RHE).

Facile Fabrication of an SnSx‐SnO2‐Decorated Cobalt Sulfide Film as an Effective Counter Electrode for Dye‐Sensitized Solar Cells

AbstractMetal sulfide stands out as one of the novel and promising platinum‐free counter electrode (CE) materials for dye‐sensitized solar cells (DSSCs). In this work, SnSx‐SnO2‐decorated CoSx films were designed and synthesized by a low‐temperature fabrication process. The small clusters of nanoparticles create a large amount of catalytic active sites, resulting in superior electrocatalytic activity for triiodide reduction. The DSSC with SnSx‐SnO2‐decorated CoSx film has achieved an impressive power conversion efficiency of 4.57 %, which is close to the efficiency of the DSSC with platinum CE (4.82 %). Furthermore, regarding the attenuation of the photovoltaic performance for the DSSC with SnSx‐SnO2‐decorated CoSx film, negligible change was observed after a prolonged storage under ambient condition for five days. Therefore, it is worthwhile to expect the explorations of novel fabricate technique for synthesizing cost‐effective metal sulfide films with long‐term stability in DSSCs.

Nanobioelectrocatalysis Using Human Liver Microsomes and Cytochrome P450 Bactosomes: Pyrenyl-Nanocarbon Electrodes.

Human liver microsomes containing various drug-metabolizing cytochrome P450 (P450) enzymes, along with their NADPH-reductase bound to phospholipid membranes, were absorbed onto 1-pyrene butylamine pi-pi stacked with amine-functionalized multiwalled carbon nanotube-modified graphite electrodes. The interfaced microsomal biofilm demonstrated direct electrochemical communication with the underlying electrode surface and enhanced oxygen reduction electrocatalytic activity typical of heme enzymes such as P450s over the unmodified electrodes and nonenzymatic currents. Similar enhancements in currents were observed when the bioelectrodes were constructed with recombinant P450 2C9 (single isoform) expressed bactosomes. The designed liver microsomal and 2C9 bactosomal bioelectrodes successfully facilitated the electrocatalytic conversion of diclofenac, a drug candidate, into 4'-hydroxydiclofenac. The enzymatic electrocatalytic metabolite yield was several-fold greater on the modified electrodes than on the unmodified bulk graphite electrodes adsorbed with a microsomal or bactosomal film. The nonenzymatic metabolite production was less than the enzymatically catalyzed metabolite yield in the designed microsomal and bactosomal biofilm electrodes. To test the throughput potential of the designed biofilms, eight-electrode array configurations were tested with the microsomal and bactosomal biofilms toward electrochemical 4'-hydroxydiclofenac metabolite production from diclofenac. The stability of the designed microsomal bioelectrode was assessed using nonfaradaic impedance spectroscopy over 40 h, which indicated good stability.

Atomic Force Microscopy (AFM) Tip based Nanoelectrode with Hydrogel Electrolyte and Application to Single-Nanoparticle Electrochemistry

<p>An unconventional fabrication technique of nanoelectrode was developed using atomic force microscopy (AFM) and hydrogel. Until now, the precise control of electroactive area down to a few nm<sup>2</sup> has always been an obstacle, which limits the wide application of nanoelectrodes. Here, the nanometer-sized contact between the boron-doped diamond (BDD) as conductive AFM tip and the agarose hydrogel as solid electrolyte was well governed by the feedback amplitude of oscillation in the non-contact mode of AFM. Consequently, this low-cost and feasible approach gives rise to new possibilities for the fabrication of nanoelectrodes. The electroactive area controlled by the set point of AFM was investigated by cyclic voltammetry (CV) of the ferrocenmethanol (FcMeOH) combined with quasi-solid agarose hydrogel as an electrolyte. Single copper (Cu) nanoparticle was deposited at the apex of the AFM tip using this platform whose electrocatalytic activity for nitrate reduction was then investigated by CV and Field Emission-Scanning Electron Microscopy (FE-SEM), respectively.</p>

N-doped lotus seedpods biocarbon hybridized with NiCo2S4 as counter electrodes for dye sensitized solar cells

A facile and green approach to composites containing nitrogen doped lotus seedpods biocarbon (NALC) and NiCo2S4 (NCS) is reported. The composites present excellent electrocatalytic activity for reduction from I3− to I− due to the synergistic effect between the nanocrystalline NCS and the NALC. Dye-sensitized solar cells (DSSCs) assembled with the as-prepared NALC@NCS counter electrodes (CEs) achieve impressive photovoltaic conversion efficiency (PCE) of 8.58%, which is higher than that by the same structured cell with Pt (7.85%) and NCS (7.53%) CEs. Compared with other NCS based CEs, the NALC@NCS CEs show good durability and stability, suggesting that combining nanocrystalline catalyst with biocarbon is beneficial to stimulate the synergistic effect, and is a feasible strategy to optimal CEs for high performance DSSCs. Low cost NALC@NCS composites developed in this work are environmentally friendly, stable and efficient, which are believed to be good candidates for Pt-free CE materials in DSSCs and electrocatalysis applications.

Improved capacitive performances and electrocatalytic reduction activity by regulating the bonding interaction between Zn-bistriazole-pyrazine/pyridine units and diverse Anderson-type polyoxometalates.

Electrochemical performances can be effectively improved by introducing metal-organic units (MOUs) into polyoxometalates (POMs). However, regulating the bonding strength between POMs and MOUs at the molecular level to improve the electrochemical performance is a challenging task. Three new POM-based metal-organic complexes (MOCs), namely H{Zn2(Hpytty)2(H2O)8[CrMo6(OH)6O18]}·2H2O (1), H{Zn2(Hpyttz)2(H2O)6[CrMo6(OH)6O18]}·8H2O (2), and {(μ2-OH)2Zn6(pyttz)2(H2O)10[TeMo6O24]}·2H2O (3) (H2pytty = 3-(pyrazin-2-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, H2pyttz = 3-(pyrid-2-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl), were obtained. Single-crystal X-ray diffraction shows that the bonding strength (from the hydrogen bond to the coordination bond) between Zn-bistriazole-pyrazine/pyridine units and diverse Anderson-type POMs gradually increases from complexes 1 to 3. Glassy carbon electrodes modified with complex 3 (3-GCE) has the highest specific capacitance, which is 930 F g-1 at 1 A g-1. Moreover, carbon paste electrodes (1-3-CPEs) modified with complexes 1-3 are used as electrochemical sensors for detecting Cr(VI) ions, with limits of detection well below the World Health Organization (WHO) maximum level in drinking water.

Electrochemical reconstruction of a 1D Cu(PyDC)(H2O) MOF into in situ formed Cu-Cu2O heterostructures on carbon cloth as an efficient electrocatalyst for CO2 conversion.

Electrochemical carbon dioxide (CO2) conversion has enormous potential for reducing high atmospheric CO2 levels and producing valuable products simultaneously; however the development of inexpensive catalysts remains a great challenge. In this work, we successfully synthesised a 1D Cu-based metal-organic framework [Cu(PyDC)(H2O)], which crystallizes in an orthorhombic system with the Pccn space group, by the hydrothermal method. Among the different catalysts utilized, the heterostructures of cathodized Cu-Cu2O@CC demonstrate increased efficiency in producing CH3OH and C2H4, achieving maximum FE values of 37.4% and 40.53%, respectively. Also, the product formation rates of CH3OH and C2H4 reach up to 667 and 1921 μmol h-1 cm-2. On the other side, Cu-Cu2O/NC-700 carbon composites simultaneously produced C1-C3 products with a total FE of 23.27%. Furthermore, a comprehensive study involving detailed DFT simulations is used to calculate the energetic stability and catalytic activity towards the CO2 reduction of Cu(111), Cu2O(111), and Cu@Cu2O(111) surfaces. During the early phase of electrochemical treatment, Cu(II) carboxylate nodes (Cu-O) in the Cu(PyDC)(H2O) MOF were reduced to Cu and Cu2O, with a possible synergistic enhancement from the PyDC ligands. Thus, the improved activity and product enhancement are closely associated with the cathodized reconstruction of Cu-Cu2O@CC heterostructures on carbon cloth. Hence, this study provides efficient derivatives of Cu-based MOFs for notable electrocatalytic activity in CO2 reduction and gives valuable insights towards the advancement of practical CO2 conversion technology.

Resorcinol-formaldehyde semiconducting resins as precursors for carbon spheres toward electrocatalytic oxygen reduction.

The carbon spheres synthesized by pyrolysis of resorcinol-formaldehyde (RF) semiconducting resins exhibit enhanced activity for electrocatalytic oxygen reduction. The spheres consist of narrow reticulated carbon layers, which are derived from the donor-acceptor π-stacking interaction of the resins, and show high electron conductivity.

Regulating intermediate adsorption and H2O dissociation on a diatomic catalyst to promote electrocatalytic nitrate reduction to ammonia

Cu–Fe–N–C demonstrates excellent electrocatalytic activity for nitrate reduction by optimizing intermediate adsorption and generating a substantial supply of H* for the thorough hydrogenation of the N-containing intermediates.

The rigidity and chelation effect of ligands on the hydrogen evolution reaction catalyzed by Ni(II) complexes.

With increasing interest in nickel-based electrocatalysts, three heteroleptic Ni(II) dithiolate complexes with the general formula [Ni(II)L(L')2] (1-3), L = 2-(methylene-1,1'-dithiolato)-5,5'-dimethylcyclohexane-1,3-dione and L' = triphenylphosphine (1), 1,1'-bis(diphenylphosphino)ferrocene (DPPF) (2), and 1,2-bis(diphenylphosphino)ethane (DPPE) (3), have been synthesized and characterized by various spectroscopic techniques (UV-vis, IR, 1H, and 31P{1H} NMR) as well as the electrochemical method. The molecular structure of complex 2 has also been determined by single-crystal X-ray crystallography. The crystal structure of complex 2 reveals a distorted square planar geometry around the nickel metal ion with a NiP2S2 core. The cyclic voltammograms reveal a small difference in the redox properties of complexes (ΔE° = 130 mV) while the difference in the catalytic half-wave potential becomes substantial (ΔEcat/2 = 670 mV) in the presence of 15 mM CF3COOH. The common S^S-dithiolate ligand provides stability, while the rigidity effect of other ligands (DPPE (3) > DPPF (2) > PPh3 (1)) regulates the formation of the transition state, resulting in the NiIII-H intermediate in the order of 1 > 2 > 3. The foot-of-the-wave analysis supports the widely accepted ECEC mechanism for Ni-based complexes with the first protonation step as a rate-determining step. The electrocatalytic proton reduction activity follows in the order of complex 1 > 2 > 3. The comparatively lower overpotential and higher turnover frequency of complex 1 are attributed to the flexibility of the PPh3 ligand, which favours the easy formation of a transition state.