Hydrogen Evolution Reaction Catalysis Research Articles

Lattice-Disordered High-Entropy Alloy Engineered by Thermal Dezincification for Improved Catalytic Hydrogen Evolution Reaction.

A disordered crystal structure is an asymmetrical atomic lattice resulting from the missing atoms (vacancies) or the lattice misarrangement in a solid-state material. It has been widely proven to improve the electrocatalytic hydrogen evolution reaction (HER) process. In the present work, due to the special physical properties (the low evaporation temperature of below 900 °C), Zn is utilized as a sacrificial component to create senary PtIrNiCoFeZn high-entropy alloy (HEA) with highly disordered lattices. The structure of the lattice-disordered PtIrNiCoFeZn HEA is characterized by the thermal diffusion scattering (TDS) in TEM. Density functional theory (DFT) calculations reveal that lattice disorder not only accelerates both the Volmer step and Tafel step during the HER process but also optimizes the intensity and distribution of projected density of states (PDOS) near the Fermi energy after the H2O and H adsorption. Anomalously high alkaline HER activity and stability are proven by experimental measurements. This work introduces a novel approach to preparing irregular lattices offering highly efficient HEA and a TDS characterization method to reveal the disordered lattice in materials. It provides a new route towards exploring and developing the catalytic activities of materials with asymmetrically disordered lattices. This article is protected by copyright. All rights reserved.

Manipulating heterointerface to boost formation and desorption of intermediates for highly efficient alkaline hydrogen evolution

Promoting water dissociation and H intermediate desorption play a pivotal role in achieving highly efficient hydrogen evolution reaction (HER) in alkaline media but remain a great challenge. Herein, we rationally develop a unique W-doped NiSx/Ni heterointerface as a favorable HER electrocatalyst which was directly grown on the Cu nanowire foam substrate (W-NiSx/Ni@Cu) by the electrodeposition strategy. Benefiting from the rational design of the interfaces, the electronic coupling of the W-NiSx/Ni@Cu can be efficiently modulated to lower the HER kinetic barrier. The obtained W-NiSx/Ni@Cu exhibits an enhanced HER activity with a low overpotential of 38 mV at 10 mA cm−2 and a small Tafel value of 27.5 mV dec−1, and high stability during HER catalysis. In addition, in-situ Raman spectra reveal that the Ni2+ active sites preferentially adsorb OH intermediate. The theoretical calculation confirms that the water dissociation is accelerated by the construction of W-NiSx/Ni heterointerface and H intermediate desorption can be also promoted by H spillover from S active sites in W-NiSx to Ni active sites in metal Ni. This work offers a valuable reference for rational designing heterointerface of electrocatalysts and provides an available method to accelerate the HER kinetics for the ampere-level current density under low overpotential.

Ordered PtNiTiZrHf nanoparticles on carbon nanotubes catalyze hydrogen evolution reaction with high activity and durability

With the scarcity of the earth's natural resources, hydrogen production from electrolyzing water is seen as an alternative energy source. Although platinum (Pt) is an advanced catalyst for hydrogen evolution reaction (HER), its application is limited by high cost and limited electrocatalytic performance. In this article, the five-element alloy nanoparticles are successfully synthesized on carbon nanotubes (CNT) by employing liquid-phase reduction and gas-phase sintering to reduce Pt utilization and improve catalytic performance. For comparison, a series of ordered and disordered (PtNi)x(TiZrHf)100-x/CNT catalysts are obtained. Results show that the ordered samples have more excellent HER catalytic performance and stability than disordered samples in 0.5 M H2SO4 and 1 M KOH electrolytes. In particular, when the electrolyte is acidic, the overpotentials of ordered (PtNi)55(TiZrHf)45/CNT at 10 and 100 mA cm−2 are 11 and 52 mV, with low Tafel slope of 37.73 mV dec−1. At 10 mA cm−2, the stabilization time can reach 58 h, which is much better than commercial Pt/C (20 wt.%). Density functional theory (DFT) calculation shows that ordered (PtNi)55(TiZrHf)45/CNT has lower hydrogen adsorption energy and activated water adsorption energy than disordered one, indicating better performance in both acidic and alkaline electrolytes. It is mainly attributed to the electronic coupling effect after ordering that makes the overall D-band center decrease. This work presents a cost-effective approach to optimize the structural design for acid-base HER electrocatalysts.

Theoretical and experimental investigations of vanadium pentoxide–based electrocatalysts for the hydrogen evolution reaction in alkaline media

AbstractA key approach towards better realization of intermittent renewable energy resources, namely, solar and wind, is green electrochemical hydrogen production from water electrolysis. In recent years, there have been increasing efforts aimed at developing noble metal-free electrocatalysts that are earth-abundant and electroactive towards hydrogen evolution reaction (HER) in alkaline electrolytes, wherein an initial water dissociation step is followed by a two-electron transfer cathodic reaction. Although relatively earth-abundant, vanadium-based electrocatalysts have been sparsely reported due to subpar electroactivity and kinetics towards water electrolysis in general and alkaline electrolysis in specific. Herein, we investigate the fine-tuning of orthorhombic V2O5-based electrocatalysts as candidates for HER through a scalable two-step sol–gel calcination procedure. Briefly, surface-induced anionic oxygen deficiencies and cationic dopants are synergistically studied experimentally and theoretically. To that end, first-principle facet-dependent density function theory (DFT) calculations were conducted and revealed that the coupling of certain dopants on V2O5 and co-induction of oxygen vacancies can enhance the catalytic HER performance by the creation of new electronic states near the Fermi level (EF), enhancing conductivity, and modulating surface binding of adsorbed protons, respectively. This was reflected experimentally through kinetically non-ideal alkaline electrochemical HER using Zn0.4V1.6O5 whereby − 194 mV of overpotential was required to attain − 10 mA/cm2 of current density, as opposed to pristine V2O5 which required 32% higher overpotential requirement at the same conditions. The disclosed work can be extended to other intrinsically sluggish transition metal (TM)–based oxides via the presented systematic tuning of surface and bulk microenvironment modulation. Graphical Abstract

Catalysis of hydrogen evolution reaction by nanocomposite electrodes composed of copper nanoparticles based on carbon quantum dots as highly efficient electrocatalyst

This study reports the synthesis, characterization, and electrochemical behavior of new non-platinum Cu-NPs/RCQDs/GCE nanocomposite. By investigating scanning electron microscopy images (SEM), the proposed and introduced nanocomposite shows spheres with an average size of less than 50 nm homogeneously dispersed on reduced carbon quantum dots (RCQDs) as an upper layer on glassy carbon electrode (GCE). Transmission electron microscopy image (TEM) of synthesized CQDs showed the small size of CQDs that was less than 20 nm. X-ray diffraction analysis (XRD) was used to investigate the crystallographic structures of electrodes. Also, the electrocatalytic treatment of catalysts toward hydrogen evolution reaction (HER) was studied in acidic media by some electrochemical techniques consisting of linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Results show that Cu-NPs/RCQDs/GCE nanocomposite with lower onset potential relative to Cu-NPs/GCE is a better electrocatalyst for reaction catalysis. Also, this proposed catalyst showed high stability and conductivity at special faradaic voltage.

Paired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp3)-H bonds using a pentacoordinated cobalt-salen catalyst

Cross-dehydrogenative coupling of C(sp3)-H bonds is an ideal approach for C(sp3)-C(sp3) bond construction. However, conventional approaches mainly rely on a single activation mode by either stoichiometric oxidants or electrochemical oxidation, which would lead to inferior selectivity in the reaction between similar C(sp3)-H bonds. Herein we describe our development of a paired electrocatalysis strategy to access an unconventional selectivity in the cross-dehydrogenative coupling of alcoholic α C(sp3)-H with allylic (or benzylic) C-H bonds, which combines hydrogen evolution reaction catalysis with hydride transfer catalysis. To maximize the synergistic effect of the catalyst combinations, a HER catalyst pentacoordinated Co-salen is disclosed. The catalyst displays a large redox-potential gap (1.98 V) and suitable redox potential. With the optimized catalyst combination, an electrochemical cross-dehydrogenative coupling protocol features unconventional chemoselectivity (C-C vs. C-O coupling), excellent functional group tolerance (84 examples), valuable byproduct (hydrogen), and high regio- and site-selectivity. A plausible reaction mechanism is also proposed to rationalize the experimental observations.

A universal and ultrafast method for fabricating a library of nanocellulose-supported metal nanoparticles

Using nanocatalysts to catalyze water electrolysis for hydrogen production is an ideal solution to address the energy crisis. The most well-adopted fabrication methods for nanocatalysts are tube furnace annealing, Hydrothermal method, etc., hardly satisfying the trade-off among coarsening, dispersity, and particle size due to mutual restrictions. Herein, a universal, ultrafast and facile cellulose nanometer whiskers-high temperature shock (CNW-HTS) method was reported for fabricating a library of ultrafine metal nanoparticles with uniform dispersion and narrow size distribution. The metal-anchor functional groups in CNW (i.e., –OH and –COOH) and the characteristics of the HTS method for ultrafast heating and powerful quenching synergistically contribute to the successful synthesis of metal nanoparticles. As an initial demonstration, the as-prepared Pt nanocatalyst (η10 ​mA ​cm−2 ​= ​51.8 ​mV) shows more excellent catalytic hydrogen evolution reaction (HER) performance than the Pt catalyst prepared in the tubular furnace (η10 ​mA ​cm−2 ​= ​169.4 ​mV). This rapid and universal CNW-HTS method can pave the way for nanomanufacturing to produce high-quality metal nanoparticles, thereby expanding applications of energy conversion and electrocatalysis.

Effect of Intrinsic Ferroelectric Phase Transition on Hydrogen Evolution Electrocatalysis

AbstractHeterogeneous electrocatalysis closely relies on the electronic structure of the catalytic materials. The ferroelectric‐to‐paraelectric phase transition of the materials also involves a change in the state of electrons that could impact the electrocatalytic activity, but such correlation remains unexplored. Here, we demonstrate experimentally and theoretically that the intrinsic electrocatalytic activity could be regulated as exampled by hydrogen evolution reaction catalysis over two‐dimensional ferroelectric CuInP2S6. The obvious discontinuity in the overpotential and apparent activation energy values for CuInP2S6 electrode are illustrated during the ferroelectric‐to‐paraelectric phase transition caused by copper displacement around Tc point (318 K), revealing the ferroelectro‐catalytic effect on thermodynamics and kinetics of electrocatalysis. When loading Pt single atom on the CuInP2S6, the paraelectric phase one showed an improved hydrogen evolution activity with smaller apparent activation energy over the ferroelectric phase counterpart. This is attributed to the copper hopping between two sulfur planes, which alternate between strong and weak H adsorption at the Pt sites to simultaneously promote H+ reactant adsorption and H2 product desorption.

A Sustainable Route to Ruthenium Phosphide (RuP)/Ru Heterostructures with Electron-Shuttling of Interfacial Ru for Efficient Hydrogen Evolution.

Ruthenium (Ru) is a promising electrocatalyst for the hydrogen evolution reaction (HER), despite suffering from low activity in non-acidic conditions due to the high kinetic energy barrier of H2O dissociation. Herein, the synthesis of carbon nanosheet-supported RuP/Ru heterostructures (RuP/Ru@CNS) from a natural polysaccharide is reported and demonstrates its behavior as an effective HER electrocatalyst in non-acidic conditions. The RuP/Ru@CNS exhibits low overpotential (106mV at 200 mA·cm-2) in alkaline electrolyte, exceeding most reported Ru-based electrocatalysts. The electron shuttling between Ru atoms at the RuP/Ru interface results in a lowered energy barrier for H2O dissociation by electron-deficient Ru atoms in the pure Ru phase, as well as optimized H* adsorption of electron-gaining Ru atoms in the neighboring RuP. A low H* spillover energy barrier between Ru atoms at the RuP/Ru interface further boosts HER kinetics. This study demonstrates a sustainable method for the fabrication of efficient Ru-based electrocatalysts and provides a more detailed understanding of interface effects in HER catalysis.

Tetrametallic mastery: Cluster-doped graphdiyne as a superior electrocatalyst for hydrogen evolution

Hydrogen evolution reaction (HER) is a promising route for sustainable hydrogen production. However, its efficiency is limited by kinetic barriers. Herein, we employ density functional theory (DFT) calculations to demonstrate a new strategy of embedding tetrametallic transition metal clusters (3TM1-TM2) into the pores of graphdiyne (GDY) to effectively optimize its HER performance. By screening 900 configurations, 10 prototypes displayed near-ideal hydrogen adsorption free energies. Among them, 3W–Hg@GDY with a ΔGH of −0.00035 eV was identified as the optimal candidate. Analysis of the electronic structure reveals hybridization between the metal d orbitals and GDY p orbitals near the Fermi level, creating partially filled impurity states to promote hydrogen adsorption. Additionally, coordination between the three TM1 atoms and active TM2 atom in the cluster enables precise tuning of TM2's electron density to achieve a moderate interaction with the adsorbed H, facilitating superior HER catalysis. Our findings showcase a new paradigm of cluster engineering for modulating GDY's reactivity that holds great promise as a universal approach for the design of high-performance GDY-based electrocatalysts beyond HER.

Effect of Intrinsic Ferroelectric Phase Transition on Hydrogen Evolution Electrocatalysis.

Heterogeneous electrocatalysis closely relies on the electronic structure of the catalytic materials. The ferroelectric-to-paraelectric phase transition of the materials also involves a change in the state of electrons that could impact the electrocatalytic activity, but such correlation remains unexplored. Here, we demonstrate experimentally and theoretically that the intrinsic electrocatalytic activity could be regulated as exampled by hydrogen evolution reaction catalysis over two-dimensional ferroelectric CuInP2S6. The obvious discontinuity in the overpotential and apparent activation energy values for CuInP2S6 electrode are illustrated during the ferroelectric-to-paraelectric phase transition caused by copper displacement around Tc point (318 K), revealing the ferroelectro-catalytic effect on thermodynamics and kinetics of electrocatalysis. When loading Pt single atom on the CuInP2S6, the paraelectric phase one showed an improved hydrogen evolution activity with smaller apparent activation energy over the ferroelectric phase counterpart. This is attributed to the copper hopping between two sulfur planes, which alternate between strong and weak H adsorption at the Pt sites to simultaneously promote H+ reactant adsorption and H2 product desorption.

Fluorination of porphyrin β-periphery boosts nickel(II)-catalyzed hydrogen evolution reaction

Tunichlorin, the naturally occurring chlorophyll cofactor containing Ni(II) ion, sets up a golden standard for designing the electrocatalysts for hydrogen evolution reaction (HER) via β-peripheral modification. Besides the fine-tuning of the porphyrin β-periphery such as adjusting the aromatics (the saturated level of tetrapyrrole) or installing hydroxyl group (hydrogen bond network) to enhance the catalytic HER efficiency, here we report that β-fluorination of porphyrin is also an important approach to increase the reactivity of Ni(II) center. Benefiting the previously reported derivatization of β-fluorinated porpholactones, we constructed a β-fluorinated tunichlorin mimic (6). Compared with the non-fluorinated analogs (1, 3, and 5), we found that 2, 4, and 6 exhibit significant electrocatalytic HER reactivity acceleration (in terms of turnover frequencies, TOF, s−1) of ca. 37, 170, 133-fold, respectively. Mechanism studies suggested that β-fluorination negatively shifts the metal complexes' reduction potentials and accelerates the electron transfer process, both contributing to the boosting of HER reaction. Notably, 6 showed an 890-fold increase of TOFs than 1, demonstrating the combining advantages of the of fluorination, hydrogenation, and hydroxylation at porphyrin β-periphery.

A Hydrogen Evolution Catalyst [Co2O2] Metallacycle Enables Regioselective Allene C(sp2)‐H Functionalization

AbstractSelective functionalization of allenic C(sp2)‐H is an ideal approach to upgrading simple allenes to synthetically useful allenes, albeit suffering from challenges associated with inert reactivity and inferior selectivity. Inspired by energy chemistry, a catalytic hydrogen evolution reaction (HER) strategy was leveraged to selectively activate weakly acidic allene C(sp2)‐H bonds in a reductive mode. An array of [Co2O2] metallacycle complexes were readily devised starting from amino acids, and they were demonstrated as robust HER catalysts, which would selectively break allenic C(sp2)‐H bonds to release hydrogen. With the newly developed HER catalyst, regioselective electrochemical functionalization of allenic C(sp2)‐H with alcoholic α C(sp3)‐H was unprecedentedly achieved. This strategy features excellent regioselectivity, unconventional chemoselectivity, good functional‐group tolerance (62 examples), and mild conditions. Mechanism experiments revealed a reactive hydroxy‐coordinated cobalt(II) species in the reaction. Density functional theory (DFT) calculations were also conducted to rationalize the regioselectivity observed in the reaction.

A Hydrogen Evolution Catalyst [Co2O2] Metallacycle Enables Regioselective Allene C(sp2)-H Functionalization.

Selective functionalization of allenic C(sp2)-H is an ideal approach to upgrading simple allenes to synthetically useful allenes, albeit suffering from challenges associated with inert reactivity and inferior selectivity. Inspired by energy chemistry, a catalytic hydrogen evolution reaction (HER) strategy was leveraged to selectively activate weakly acidic allene C(sp2)-H bonds in a reductive mode. An array of [Co2O2] metallacycle complexes were readily devised starting from amino acids, and they were demonstrated as robust HER catalysts, which would selectively break allenic C(sp2)-H bonds to release hydrogen. With the newly developed HER catalyst, regioselective electrochemical functionalization of allenic C(sp2)-H with alcoholic α C(sp3)-H was unprecedentedly achieved. This strategy features excellent regioselectivity, unconventional chemoselectivity, good functional-group tolerance (62 examples), and mild conditions. Mechanism experiments revealed a reactive hydroxy-coordinated cobalt(II) species in the reaction. Density functional theory (DFT) calculations were also conducted to rationalize the regioselectivity observed in the reaction.

Boosting hydrogen evolution kinetics of self-supported MoC-Mo2C heterojunction electrode by platinum decoration

Molybdenum carbide-based hydrogen evolution reaction (HER) electrocatalysts have attracted widespread attention with their low cost and relatively high catalytic activity. Despite the significant progress made in tuning the morphology and structure, the intrinsic catalytic activity of molybdenum carbide awaits further improvement. Herein, a Pt-decorated self-supported MoC-Mo2C electrode with super-intrinsic HER catalytic activity is prepared by a simple adsorption-electroreduction method. The HER performance is improved with increasing the loading of Pt. The optimal MoC-Mo2C-Pt heterojunction electrode has a low overpotential of 10 mA cm−2 (58 mV in H2SO4, 82 mV in KOH) and small Tafel slope (24 mV dec−1 in H2SO4, 29 mV dec−1 in KOH), which is reduced to 0.45–0.5, 0.7–0.8, and 0.4–0.7 times of pristine MoC-Mo2C, Pt foil, and commercial Pt/C (2 mg cm−2), respectively. The improved HER catalysis is attributed to the rapid dissociation of water on MoC-Mo2C and efficient desorption of hydrogen on Pt. Therefore, decorating carbides with Pt is an effective way to design HER catalysts with enhanced catalytic activities in a wide pH range.

Synergistic Co-MOF/ZnS Composite: Advancing Supercapattery Performance and Catalyzing Hydrogen Evolution Reaction

Synergistic Co-MOF/ZnS Composite: Advancing Supercapattery Performance and Catalyzing Hydrogen Evolution Reaction

Defect engineering of 1T′ MX 2 (M = Mo, W and X = S, Se) transition metal dichalcogenide-based electrocatalyst for alkaline hydrogen evolution reaction

The alkaline electrolyzer (AEL) is a promising device for green hydrogen production. However, their energy conversion efficiency is currently limited by the low performance of the electrocatalysts for the hydrogen evolution reaction (HER). As such, the electrocatalyst design for the high-performance HER becomes essential for the advancement of AELs. In this work, we used both hydrogen (H) and hydroxyl (OH) adsorption Gibbs free energy changes as the descriptors to investigate the catalytic HER performance of 1T′ transition metal dichalcogenides (TMDs) in an alkaline solution. Our results reveal that the pristine sulfides showed better alkaline HER performance than their selenide counterparts. However, the activities of all pristine 1T′ TMDs are too low to dissociate water. To improve the performance of these materials, defect engineering techniques were used to design TMD-based electrocatalysts for effective HER activity. Our density functional theory results demonstrate that introducing single S/Se vacancy defects can improve the reactivities of TMD materials. Yet, the desorption of OH becomes the rate-determining step. Doping defective MoS2 with late 3d transition metal (TM) atoms, especially Cu, Ni, and Co, can regulate the reactivity of active sites for optimal OH desorption. As a result, the TM-doped defective 1T′ MoS2 can significantly enhance the alkaline HER performance. These findings highlight the potential of defect engineering technologies for the design of TMD-based alkaline HER electrocatalysts.

Reduction mechanism of hydrothermally synthesized wide band gap ZnWO4 nanorods for HER application

This manuscript presents a detailed investigation of the synthesis of zinc tungstate (ZnWO4) nanoparticles and various characterizations of the as-synthesized sample to reveal its potential for hydrogen evolution reaction (HER). The study focuses on a simple and efficient hydrothermal method that facilitates the production of ZnWO4 nanoparticles, which involves the controlled reaction between zinc and tungstate ions in a specific solution. The resulting ZnWO4 nanoparticles were characterized by various characterization techniques which include XRD, UV-vis spectroscopy, TEM and electrochemical study to get insights into their size, structure, properties and electrochemical behaviour. The characterization includes the analysis of the nanoparticles' structural features and optical properties. The material’s electrochemical properties were also investigated by employing cyclic voltammetry (CV) and potentio electrochemical impedance spectroscopy (PEIS). The charge transfer process was studied for the material revealing its diffusion controlled behaviour and reduction peaks in the cathodic region. These properties suggest that the material is a potential candidate for HER catalysis.

Structure transformation induced bi-component Co–Mo/A-Co(OH)2 as highly efficient hydrogen evolution catalyst in alkaline media

Elucidating the inherent origins of the sluggish hydrogen evolution reaction (HER) kinetics in alkaline media and developing high-performance electrocatalysts are fundamental for the advances of conventional alkaline water electrolyzers and emerging anion exchange membrane (AEM) electrolyzers. Here we present a facile electrochemical modification strategy for the synthesis of bi-component Co–Mo(18%)/A-Co(OH)2 catalyst toward efficient HER catalysis in alkaline media. Porous Co–Mo alloys with adjustable Mo/Co atomic ratio are first prepared by H2-assisted cathodic electrodeposition. By virtue of the appropriate electronic structure and hydrogen binding energy, Co–Mo(18%) is the most HER active among the alloys and is further activated by a constant-current electrochemical modification process. Physical characterizations reveal the formation of amorphous Co(OH)2 nanoparticles on the surface. Electrokinetic analysis combined with theoretical calculations reveal that the in-situ formed Co(OH)2 can efficiently promote the water dissociation, resulting in accelerated Volmer-step kinetics. As a result, the Co–Mo(18%)/A-Co(OH)2 simultaneously achieves the optimization of the two factors dominating alkaline HER activity, i.e., water dissociation and hydrogen adsorption/desorption via the bifunctional synergy of the bi-components. The high HER activity (η10 of 47 ​mV at 10 ​mA ​cm−2) of Co–Mo(18%)/A-Co(OH)2 is close to benchmark Pt/C catalyst and comparable or superior to the most active non-noble metal catalysts.

Exploring the effect of a pendent amine group poised over the secondary coordination sphere of a cobalt complex on the electrocatalytic hydrogen evolution reaction.

A CoIII complex (2) of a bispyridine-dioxime ligand (H2LNMe2) containing a tertiary amine group in the proximity of the Co center is synthesized and characterized. One of the oxime protons of the ligand is deprotonated, and the amine group remains protonated in the solid-state structure of the CoII complex (2a). The acid-base properties of 2 showed pKa values of 5.9, 8.4, and 9.6, which are assigned to the dissociation of two consecutive oxime protons and amine protons, respectively. The electrocatalytic proton reduction of 2 was investigated in an aqueous phosphate buffer solution (PBS), revealing a catalytic hydrogen evolution reaction (HER) at an Ecat/2 of -1.01 V vs. the SHE, with an overpotential of 673 mV and a kobs value of 2.6 × 103 s-1 at pH 7. For comparison, the HER of the Co complex (1) lacking the tert-amine group at the secondary sphere was investigated in PBS, which showed a kobs of 1.3 × 103 s-1 and an overpotential of 577 mV. At pH 4, however, 2 revealed a ∼3 times higher kobs value than 1, which suggests that the protonated amine group likely works as a proton relay site. Notably, no significant change in the reaction rate was observed at different pH values for 1, implying that oxime protons may not be involved in the intramolecular proton-coupled electron transfer reaction in the HER. The kobs values for Co complexes at pH 7.0 are significantly higher than those of the [Co(dmgH)2(pyridine)(Cl)] complex, implying that the primary coordination sphere around 1 or 2 enhances the HER and offers better catalyst stability in acidic buffer solutions.