Non-precious Metal-based Catalysts Research Articles

Revealing Structural Evolution of Nickel Phosphide-Iron Oxide Core-Shell Nanocatalysts in Alkaline Medium for the Oxygen Evolution Reaction.

Metal phosphide-containing materials have emerged as a potential candidate of nonprecious metal-based catalysts for alkaline oxygen evolution reaction (OER). While it is known that metal phosphide undergoes structural evolution, considerable debate persists regarding the effects of dynamics on the surface activation and morphological stability of the catalysts. In this study, we synthesize NiP x -FeO x core-shell nanocatalysts with an amorphous NiP x core designed for enhanced OER activity. Using ex situ X-ray absorption spectroscopy, we elucidate the local structural changes as a function of the cyclic voltammetry cycles. Our studies suggest that the presence of corner-sharing octahedra in the FeO x shell improves structural rigidity through interlayer cross-linking, thereby inhibiting the diffusion of OH-/H2O. Thus, the FeO x shell preserves the amorphous NiP x core from rapid oxidation to Ni3(PO4)2 and Ni(OH)2. On the other hand, the incorporation of Ni from the core into the FeO x shell facilitates absorption of hydroxide ions for OER. As a result, Ni/Fe(OH) x at the surface oxidizes to the active γ-(oxy)hydroxide phase under the applied potentials, promoting OER. This intriguing synergistic behavior holds significance as such a synthetic route involving the FeO x shell can be extended to other systems, enabling manipulation of surface adsorption and diffusion of hydroxide ions. These findings also demonstrate that nanomaterials with core-shell morphologies can be tuned to leverage the strength of each metallic component for improved electrochemical activities.

Crystal phase engineering of CoBOx/NiCoP heterostructures as trifunctional electrocatalysts for overall water splitting and urea electrolysis

Rational design of non-precious metal-based catalysts for value-added chemicals production is crucial but still challenging. Herein, a trifunctional electrocatalyst with heterostructures is developed via phosphating and NaBH4 pretreatment of the pristine ZIF-L for overall water splitting and urea oxidation. The as-prepared CoBOx/NiCoP catalyst exhibits superior electrocatalytic performance with only overpotentials of 100, 283 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) to reach the current density of 10 and 100 mA cm−2, respectively, and the low potential of 1.35 V to achieve a current density of 100 mA cm−2 for urea oxidation reaction (UOR). Theoretical calculations show that the construction of amorphous/crystalline heterostructure can accelerate the charge transfer between the active site and intermediate, thus enhance the intermediates adsorption and reduce the kinetic barrier toward HER/OER process for enhancing electrocatalytic activity. Importantly, the in-situ Raman spectroscopy discloses that the rapid formation of oxidation-state transition metal oxyhydroxide species would provide more active sites for the oxidation reaction. This multiple electrocatalysis demonstrates the great potential of amorphous/crystalline heterogeneous interfaces for high-performing electrocatalytic conversions.

Non-precious Electrocatalysts for the Hydrogen Evolution Reaction

The development of non-precious metal-based catalysts for the hydrogen evolution reaction (HER) is a promising research area with the potential to advance water electrolysis and enable the widespread use of hydrogen as a clean energy source. While noble metals like Pt and Pd exhibit excellent HER activity, their limited availability and high cost present significant challenges. Non-precious transition metals such as Fe, Co, and Ni have emerged as alternative catalyst materials due to their natural abundance. However, these metals often encounter obstacles related to their hydrogen adsorption behavior. This commentary highlights the various strategies employed to optimize the electronic structures of non-precious metal-based catalysts to enhance the HER performance. The outlook of non-precious metal-based catalysts is bright, with ongoing and future research activities mainly focusing on improving their properties, integrating these catalysts into commercial water electrolysis systems, and improving the scalability for large-scale hydrogen production. The development of high-performance non-precious metal-based catalysts for HER is crucial to future sustainable and efficient hydrogen production in the transition from fossil fuels to clean energy.

A Review of the Structure–Property Relationship of Nickel Phosphides in Hydrogen Production

Hydrogen, one of the most promising forms of new energy sources, due to its high energy density, low emissions, and potential to decarbonize various sectors, has attracted significant research attention. It is known that electrocatalytic hydrogen production is one of the most widely investigated research directions due to its high efficiency in the conversion of electricity to H2 gas. However, given the limited reserves and high cost of precious metals, the search for non-precious metal-based catalysts has been widely explored, for example, transition metal phosphides, oxides, and sulfides. Despite this interest, a detailed survey unveils that the surface and internal structures of the alternative catalysts, including their surface reconstruction, composition, and electronic structure, are poorly studied. As a result, a disconnection in the structure–property relationship severely hinders the rational design of efficient and reliable non-precious metal-based catalysts. In this review, by focusing on Ni5P4, a bifunctional catalyst for water splitting, we systematically summarize the material motifs pertaining to the different synthetic methods, surface characteristics, and hydrolysis properties. It is believed that a cascaded correlation may provide insights toward understanding the fundamental catalytic mechanism and design of robust alternative catalysts for hydrogen production.

Bio-extract mediated green synthesis of bi-functional ammonium cobalt phosphate nanoflakes electrode/catalyst for supercapattery and ethanol oxidation

The present study proposes a low-cost, green technique to the synthesis of bi-functional ammonium cobalt phosphate for energy storage and conversion applications. The comprehensive physiochemical investigations are carried out using various spectral-analytical techniques. The results of phase and surface morphology confirm the formation of an orthorhombic crystal structure with flakes-like microstructure. With a maximal specific capacity of 448.3 mAhg−1 at 2 mAcm−2, bio-solvent driven NH4CoPO4·H2O with graphene oxide (GO) nanoflakes demonstrates exceptional battery-type energy storage capabilities. As constructed supercapattery device exhibits a high specific energy of 85.4 Wh kg−1 at power output of 1283 W kg−1 and 81 % stability after 5000 cycles. Further exploration as a non-precious metal-based catalyst for ethanol oxidation reaction (EOR), NH4CoPO4·H2O /GO showed a high peak current density of 83.4 mAcm−2 at 20 mVs−1. Coupled oxygen/hydrogen evolution processes are investigated in 1 M KOH in order to acquire a better understanding of the catalyst's EOR activity. The NH4CoPO4·H2O/GO sample exhibited the lowest overpotentials of |ηOER@10| = 420 mV, and |ηHER@10| = 112 mV, with Tafel slopes of 169.8 mV dec−1 for OER and 132.8 mV dec-1 for HER, respectively. This is due to the catalyst's slow OH adsorption during OER and the limited H*recombination during HER. Therefore, this approach provides a green and cost-effective method to synthesis efficient bi-functional electrode/catalysts for supercapattery and alkaline fuel cells.

Two-dimensional flake Co/Co2N0.67 modified by molybdenum oxides achieves enhancement of bifunctional hydrogen electrocatalysis

To address the urgent need for non-precious metal-based catalysts in the industrial preparation and application of hydrogen energy, we present a secondary hydrothermal strategy to prepare a Mo-modified cobalt carbonate precursor, resulting in the Mo–Co/Co2N0.67 catalyst. The cobalt-based materials exhibit a layered flake structure due to molybdenum modification, exposing more active sites, while molybdenum oxide modification enhances hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). In alkaline HER measurements, Mo–Co/Co2N0.67 achieves a remarkable current density of 10 mA cm−2 at only 27 mV. The overall water splitting of Mo–Co/Co2N0.67 + RuO2 can reach 10 mA cm−2 at 1.52 V voltage. In alkaline HOR measurements, it exhibits the current density of 2.92 mA cm−2@0.1 V vs. RHE and an exchange current density (J0) of 2.96 mA cm−2. This work highlights the effective regulation of non-noble metal-based electrocatalysts through Mo modification, providing valuable insights for the development of efficient non-precious metal-based hydrogen electrocatalysis within the context of anion exchange membrane unitized reversible fuel cells (AEM-URFC).

Agglomeration inhibition engineering of nickel–cobalt alloys by a sacrificial template for efficient urea electrolysis

Designing efficient non-precious metal-based catalysts for urea oxidation reaction (UOR) is essential for achieving energy-saving hydrogen production and the treatment of wastewater containing ammonia. In this study, sodium dodecyl sulfate (SDS) is employed as a sacrificial template to synthesize NiCo alloy nanowires (NiCo(SDS)/CC), and the instinct formation mechanism is investigated. It is found that SDS can inhibit the Ostwald ripening during hydrothermal and calcination processes, which could release abundant active cobalt, thereby modulating the electronic structure to promote the catalytic reaction. Moreover, SDS as a sacrificial template can induce the deposition of metal atoms and increase the specific surface area of the catalyst, providing abundant active sites to accelerate the reaction kinetics. As expected, the NiCo(SDS)/CC exhibits good activity for both UOR and hydrogen evolution reactions (HER) and it requires only 1.31 V and −86 mV to obtain a current density of ±10 mA cm−2, respectively. This work provides a new strategy for reducing the agglomeration of transition metals to design high-performance composite catalysts for urea oxidation.

Tuning the selectivity of the CO2 hydrogenation reaction using boron-doped cobalt-based catalysts.

Direct CO2 hydrogenation to value-added chemicals is a promising path toward realizing the "carbon-neutral" goal. However, controlling the selectivity of CO2 hydrogenation toward desired products (e.g., CO and CH4) using non-precious metal-based catalysts is important but challenging. It is imperative to explore catalysts with high activity and stability. Herein, boron-doped cobalt nanoparticles supported on H-ZSM-5 were devised for CO2 hydrogenation to produce CO in a gas-solid flow system. Our results demonstrate that boron doping not only increases the CO2 adsorption capability of the catalyst but also optimizes the electronic state of Co for CO desorption during hydrogenation process. As a result, the boron-doped cobalt catalysts displayed an enhanced CO selectivity of 94.5% and a CO2 conversion rate of 45.6%, which is much higher than that of Co-ZSM-5 without boron doping. This study shows that the strategic design of metal borides is important for controlling the selectivity of desired products in the CO2 hydrogenation reaction.

Boosting Oxygen Reduction Reaction with Fe-Based Single-Atom Catalysts: The Role of Cluster Interactions

Fuel cells (FCs) have emerged as a promising alternative for efficient electricity production in the future [1]. However, their widespread commercialization is hindered by their prohibitive cost due to the large amount of platinum used in these electrochemical systems [2]. Platinum is used to accelerate the unfavorable kinetics of the cathodic oxygen reduction reaction (ORR) [3]. To achieve large-scale and cost-effective development of FCs, it is essential to find high-performance platinum-free catalysts. Two solutions are mainly reported in the literature: the development of non-precious metal-based carbon catalysts and metal-free carbon catalysts. However, the work reported on these two types of carbon catalysts is sometimes contradictory regarding the actual nature of the active sites and the mechanisms of reduction of oxygen molecules on the catalyst [4].Pyrolyzed metal-nitrogen-carbon (M-N-C) catalysts for the ORR, especially single-atom catalysts (SACs), have been widely studied because they exhibit excellent electrocatalytic performance, thanks to the high content of metal atoms anchored on a carbon support [5]. Recent research has indicated that the combination of single-atom active sites with metal nanoclusters can further improve the catalytic activity, but the underlying mechanism remains unclear [6]. Therefore, it is necessary to develop model catalysts based on both single-atoms and nanoclusters to better understand their catalytic activity.In this work, we prepared nitrogen-doped and iron-doped carbon catalysts (called Fe-NC below) with precise control of the type of iron in the material. First, the functionalization of an activated carbon was performed by carbonizing it under air in the presence of urea. Then, the sample was placed in an autoclave for hydrothermal treatment in the presence of FeCl3.6H2O to allow the incorporation of iron, and thermal post-treatment was applied to synthesize model catalysts (Fig. 1a). The precursor ratio and final pyrolysis temperature were adjusted and optimized to produce either iron-based single atoms (SA) (here referred to as FeSA-NC) or atomic clusters (AC) associated with single atoms (here referred to as FeSA+AC-NC). The results show that the iron-based catalysts exhibit outstanding catalytic activity (Fig. 1b) and durability (Fig. 1c) in alkaline medium for the ORR, even better than commercial Pt (20 wt.%)/C in the case of FeSA+AC-NC. The analysis provided insight into the development of highly efficient multifunctional electrocatalysts, where the presence of iron nanoclusters was found to be a crucial determinant of the catalytic activity for the ORR.[1] M.K. Debe, Electrocatalyst approaches and challenges for automotive fuel cells, Nature. 486 (2012) 43–51. https://doi.org/10.1038/nature11115.[2] C. Sealy, The problem with platinum, Mater. Today. 11 (2008) 65–68. https://doi.org/10.1016/S1369-7021(08)70254-2.[3] M. Borghei, J. Lehtonen, L. Liu, O.J. Rojas, Advanced Biomass-Derived Electrocatalysts for the Oxygen Reduction Reaction, Adv. Mater. 30 (2018) 1703691. https://doi.org/10.1002/adma.201703691.[4] A. Dessalle, J. Quílez-Bermejo, V. Fierro, F. Xu, A. Celzard, Recent progress in the development of efficient biomass-based ORR electrocatalysts, Carbon. 203 (2023) 237–260. https://doi.org/10.1016/j.carbon.2022.11.073.[5] K. Liu, J. Fu, Y. Lin, T. Luo, G. Ni, H. Li, et al., Insights into the activity of single-atom Fe-N-C catalysts for oxygen reduction reaction, Nat. Commun. 13 (2022) 2075. https://doi.org/10.1038/s41467-022-29797-1.[6] X. Wan, Q. Liu, J. Liu, S. Liu, X. Liu, L. Zheng, et al., Iron atom–cluster interactions increase activity and improve durability in Fe–N–C fuel cells, Nat. Commun. 13 (2022) 2963. https://doi.org/10.1038/s41467-022-30702-z. Figure 1

Rational design of bimetal phosphide embedded in carbon nanofibers for boosting oxygen evolution

The development of non-precious metal electrocatalysts for oxygen evolution reaction (OER) is crucial for generating large-scale hydrogen through water electrolysis. In this work, bimetal phosphides embedded in electrospun carbon nanofibers (P-FeNi/CNFs) were fabricated through a reliable electrospinning–carbonization–phosphidation strategy. The incorporation of P-FeNi nanoparticles within CNFs prevented them from forming aggregation and further improved their electron transfer property. The bimetal phosphides helped to weaken the adsorption of O intermediate, promoting the OER activity, which was confirmed by the theoretical results. The as-prepared optimized P-Fe1Ni2/CNFs catalyst exhibited very high OER electrocatalytic performance, which required very low overpotentials of just 239 and 303 mV to reach 10 and 1000 mA cm−2, respectively. It is superior to the commercial RuO2 and many other related OER electrocatalysts reported so far. In addition, the constructed alkaline electrolyzer based on the P-Fe1Ni2/CNFs catalyst and Pt/C delivered a cell voltage of 1.52 V at 10 mA cm−2, surpassing the commercial RuO2||Pt/C (1.61 V) electrolyzer. It also offered excellent alkaline OER performance in simulated seawater electrolyte. This demonstrated its potential for practical applications across a broad range of environmental conditions. Our work provides new ideas for the ration design of highly efficient non-precious metal-based OER catalysts for water electrolysis.

Fe&Fe2O3 Dual-Decorated on N-Doped Porous Carbon for Oxygen Reduction Reaction

Catalysts for the cathodic oxygen reduction reaction (ORR) are important in fuel cells. Herein, a class of non-precious metal ORR catalyst, namely Fe&Fe2O3 dual-decorated on N-doped porous carbon (Fe&Fe2O3/NC), is prepared from the pyrolysis of a mixture containing Fe2O3/NC, Fe salt and melamine, followed by acid-leaching, where Fe2O3/NC is firstly synthesized from one-step pyrolyzing the precursors of coal, KOH, melamine and Fe salt. As a result, the Fe&Fe2O3/NC provides a much better ORR catalytic activity with the peak potential (Ep) and half-wave potential (E1/2) of 902 mV and 852 mV, respectively, than these of Fe2O3/NC (824 mV and 768 mV) and close to these of 20 wt% commercial Pt/C (918 mV and 863 mV). Furthermore, the ORR occurred on Fe&Fe2O3/NC follows near a four-electron transfer pathway. It also has a good stability and methanol-resistance. By comparing the structures of Fe2O3/NC and Fe&Fe2O3/NC, the essential roles on improving the ORR catalytic activity are discussed: both the abundant graphitic N active sites and the synergistic effect of Fe and Fe2O3 play important roles. This work not only provides a general guideline for the design and development of non-precious metal-based catalysts for ORR but also enriches the application scope of coal.

Progress of ultrafine noble metal nanocatalysts regulated by confining engineering for water electrolysis

Water electrolysis has been considered a promising technology for producing sustainable green hydrogen fuel energy. Noble metal nanocatalysts have exhibited widely recognized activities for electrocatalysis. However, the high cost of producing hydrogen by noble metal limits the widespread adoption of this fuel. The key to reducing the usage lies in reducing the size of noble metals to the atomic scale to offer rich active sites and unique electronic structures to enhance their catalytic activity. Generally, the charge transfer between the host support and guest materials by confining engineering can improve the catalytic activity, as well as overcome the aggregation and/or structural degradation of guests. In contrast to previous reviews involving electrochemistry under confinement, or confined nonprecious metal-based catalysts, our review offers a scientific analysis of the structure–activity relationship in the development of platinum group metals via confinement engineering for water splitting. Our discussion covers diverse confinement strategies including space confinement, space-electrostatic confinement, and space-coordination confinement with a special focus on the advances in the coordination-confinement (pyrolysis) strategy for ultrafine noble metal nanostructures. Finally, we put forward future development directions including hydrogen spillover path, in situ characterization, and electrical double layer atomic/molecule structure analysis in confined metal-based electrocatalysts for water electrolysis.

Laser Synthesis of Nonprecious Metal-Based Single-Atom Catalysts for Oxygen Reduction Reaction.

Development of nonprecious metal-based single-atom catalysts (SACs) has provided opportunities to substitute Pt group metals and offer maximum atom utilization and unique coordination environments. Among these catalysts, Fe-N-C catalysts with atomically dispersed Fe-N4 active sites have emerged as some of the most promising oxygen reduction reaction (ORR) catalysts. However, furnace synthesis of Fe-N-C catalysts with carbon substrate derived from metal-organic framework (MOF) involves a high-temperature procedure, in which nitrogen from the carbonized MOF tends to be removed, subsequently leading to a low density of active sites. In this work, we developed a rapid and simple solid-state route to fabricate SACs through laser-induced thermal activation (LITA) of carbonized zeolitic imidazolate framework-8 (ZIF-8) adsorbed with Fe precursors. The results demonstrate that the laser process effectively avoids the loss of nitrogen in the nitrogen-doped carbon substrate and achieves a loading of Fe single atoms of 2.3 wt %, in comparison with that of 1.2 wt % from the conventional furnace treatment. The Fe-N-C catalyst synthesized in the study presents a half-wave potential of 0.91 V for ORR in alkaline media, which is higher than that of commercial Pt/C (0.87 V). When used as a cathode catalyst in zinc-air batteries (ZABs), the battery exhibits excellent electrochemical performance. This work also demonstrates the versatility of the technique through the successful synthesis of Co-N-C and Ni-N-C single atoms on nitrogen-doped carbon substrates.

Research Progress of Perovskite-Based Bifunctional Oxygen Electrocatalyst in Alkaline Conditions.

In light of the depletion of conventional energy sources, it is imperative to conduct research and development on sustainable alternative energy sources. Currently, electrochemical energy storage and conversion technologies such as fuel cells and metal-air batteries rely heavily on precious metal catalysts like Pt/C and IrO2, which hinders their sustainable commercial development. Therefore, researchers have devoted significant attention to non-precious metal-based catalysts that exhibit high efficiency, low cost, and environmental friendliness. Among them, perovskite oxides possess low-cost and abundant reserves, as well as flexible oxidation valence states and a multi-defect surface. Due to their advantageous structural characteristics and easily adjustable physicochemical properties, extensive research has been conducted on perovskite-based oxides. However, these materials also exhibit drawbacks such as poor intrinsic activity, limited specific surface area, and relatively low apparent catalytic activity compared to precious metal catalysts. To address these limitations, current research is focused on enhancing the physicochemical properties of perovskite-based oxides. The catalytic activity and stability of perovskite-based oxides in Oxygen Reduction Reaction/Oxygen Evolution Reaction (ORR/OER) can be enhanced using crystallographic structure tuning, cationic regulation, anionic regulation, and nano-processing. Furthermore, extensive research has been conducted on the composite processing of perovskite oxides with other materials, which has demonstrated enhanced catalytic performance. Based on these different ORR/OER modification strategies, the future challenges of perovskite-based bifunctional oxygen electrocatalysts are discussed alongside their development prospects.

Core–shell heterostructure engineering of CoP nanowires coupled NiFe LDH nanosheets for highly efficient water/seawater oxidation

Searching for efficient nonprecious metal-based catalysts toward oxygen evolution reaction (OER) are of significance for seawater electrolysis. Herein, a core–shell-structured hybrid of cobalt phosphide nanowires@NiFe layered double hydroxide nanosheets grown on conductive nickel foam (CoP@NiFe LDH/NF) is prepared by a feasible approach at low temperature. The charming structure can provide numerous phosphide/hydroxide heterogenous interfaces, expose abundant active sites, and boost electron/mass transfer, synergistically enhancing catalytic OER activity. When employed as an electrocatalyst toward the OER, the resultant CoP@NiFe LDH/NF only requires a small overpotential of 287 mV to provide 300 mA/cm2 current density as well as long-time durability in 1.0 mol/L KOH seawater. The regulation of electronic states and surface reconstruction synergistically contribute to highly efficient seawater oxidation. This work provides an opportunity to construct efficient and inexpensive electrocatalysts for hydrogen production.

Reduced Graphene Oxide-Supported Iron-Cobalt Alloys as High-Performance Catalysts for Oxygen Reduction Reaction.

Exploring non-precious metal-based catalysts for oxygen reduction reactions (ORR) as a substitute for precious metal catalysts has attracted great attention in recent times. In this paper, we report a general methodology for preparing nitrogen-doped reduced graphene oxide (N-rGO)-supported, FeCo alloy (FeCo@N-rGO)-based catalysts for ORR. The structure of the FeCo@N-rGO based catalysts is investigated using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and transition electron microscopy, etc. Results show that the FeCo alloy is supported by the rGO and carbon that derives from the organic ligand of Fe and Co ions. The eletrocatalytic performance is examined by cyclic voltammetry, linear scanning voltammetry, Tafel, electrochemical spectroscopy impedance, rotate disc electrode, and rotate ring disc electrode, etc. Results show that FeCo@N-rGO based catalysts exhibit an onset potential of 0.98 V (vs. RHE) and a half-wave potential of 0.93 V (vs. RHE). The excellent catalytic performance of FeCo@N-rGO is ascribed to its large surface area and the synergistic effect between FeCo alloy and N-rGO, which provides a large number of active sites and a sufficient surface area.

In-situ fabrication of bimetallic FeCo2O4-FeCo2S4 heterostructure for high-efficient alkaline freshwater/seawater electrolysis

Rational construction of bifunctional electrocatalysts with long-term stability and high electrocatalytic activity is of great importance, but it is challenging to obtain highly efficient non-precious metal-based catalysts for overall seawater electrolysis. Herein, a nickel foam (NF) self-supporting CoFe-layered double hydroxide (CoFe-LDH/NF) was directly converted into FeCo2O4-FeCo2S4 heterostructure via hydrothermal method in 50 mM Na2S solution, instead of FeCo2O4@FeCo2S4 core-shell structure. The FeCo2O4-FeCo2S4 heterojunction shows nanosheets structure with rough surface (the thickness of ∼ 198.9 nm), which provides rich oxide/sulfide interfaces, high electrochemical active area, a large number of active sites, as well as fast charge and mass transfer. In 1.0 M KOH solution, 1.0 M KOH + 0.5 M NaCl, and alkaline natural seawater, the FeCo2O4-FeCo2S4 heterojunction exhibits eminently electrocatalytic performance, with overpotentials of η-100 = 225 mV, η-100 = 233 mV, and η-100 = 238 mV for OER, as well as η-100 = 271 mV, η-100 = 273 mV, and η-100 = 277 mV for HER, respectively. Furthermore, self-supporting FeCo2O4-FeCo2S4 electrode (FeCo2O4-FeCo2S4/NF) as the cathode and anode of an electrolyzer exhibits a lower cell voltage of E-100 = 1.75 V in alkaline seawater than those of FeCo2S4/NF (1.77 V), CoFe-LDH/NF (1.87 V), and FeCo2O4/NF (1.91 V). Specifically, FeCo2O4-FeCo2S4 electrolyzer can stably produce hydrogen for over 48 h in alkaline freshwater/seawater electrolyte. These outstanding electrocatalytic performances and corrosion resistance to salty-water can be attributed to the surface reconstruction behavior of the FeCo2O4-FeCo2S4/NF catalyst during OER, which leads to the in-situ formation of metal oxyhydroxides. In particular, the FeCo2O4-FeCo2S4 heterojunction is also very competitive among most state-of-the-art non-noble metal-based catalysts, whether in KOH or alkaline salty-water electrolytes.

Al-doping-induced electronic structure modulation of CoSe2 for efficient hydrogen evolution reaction

The development of highly efficient, long-lasting, and earth-rich electrocatalysts for hydrogen evolution processes (HER) is crucial to the advancement of hydrogen energy. Due to its improved catalytic activity, extraordinary chemical stability, and low cost, pyrite cobalt selenide (CoSe2) has become an incredibly potential replacement for Pt-based HER electrocatalysts. However, because of limited hydrogen adsorption and accompanying restrictions in its electronic structure, its practical application has run into difficulties. Herein, we have introduced aluminum (Al) into CoSe2/CC nanowire arrays on carbon cloth using a simple hydrothermal and selenization method. The synthesized materials serve as highly effective catalysts for HER, with the optimized Al-CoSe2/CC demonstrating a significantly overpotential reduced by nearly 90 mV compared to pure CoSe2/CC (from 243 mV to 153 mV) at a current density at 10 mA cm−2 and a small Tafel slope of 88 mV dec−1. Moreover, these catalysts exhibit exceptional durability, sustaining their performance for 24 h. Based on the experimental results and subsequent density functional theory (DFT) calculations, it has been demonstrated that Al doping can significantly enhance the electronic conductivity, maximize the hydrogen evolution adsorption energy, and improve the charge transfer ability. This work offers a profound insight into the correlation between cation substitution in non-precious metal-based catalysts and the enhancement of intrinsic HER catalytic performance.

Sustainable bacterial cellulose derived composites for high-efficiency hydrogen evolution reaction

Incorporating heteroatoms into carbon structure has been demonstrated to be efficient for hydrogen evolution reaction (HER). However, the preparation complexity and poor durability are insufficient for the future hydrogen economy. In this work, the preparation of ZIF-67/BC precursor with BC as the template was done for the in-situ growth of MOFs (ZIF-67) crystals, followed by the carbonization and phosphating of ZIF-67/BC to prepare the CoP-NC/CBC N-doped composite carbon material with CoP as the primary active material. The results show that as an HER catalyst, CoP-NC/CBC can provide a current density of 10 mA cm−2 at an overpotential of 182 mV in the acidic electrolyte of 0.5 M H2SO4 or the same current density at an overpotential of 151 mV in the alkaline electrolyte of 1.0 M KOH. The work validates a design idea for advanced non-precious metal-based HER catalysts with high activity and stability.

Alkaline hydrogen production promoted by small-molecule modification on flowerlike Co2(OH)2CO3

Developing a low-cost and high-efficiency nonprecious metal-based catalyst for hydrogen evolution reaction (HER) is of great significance for the utilization of hydrogen energy. In this work, we report a molecular-modification strategy to fabricate a self-supported hydrogen evolution electrode, specially by grafting the macrocyclic molecules (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) on the surface of a cobaltous dihydroxycarbonate (COC) seed layer. The HHTP-COC electrode is endowed with a rod-like structure, which provides favorable access for charge transportation and mass exchange. The macrocyclic molecule structure in HHTP can be grafted on COC and improve the electrical conductivity, while the interaction between HHTP and COC induces the rearrangement of charge configuration on the surface. Due to the combination effects of several aspects, the HHTP-COC electrode achieves astonishing HER activity, with a low overpotential of 61.0 mV (η10, at the current density of 10 mA cm−2) and excellent stability in alkaline condition. This kind of interface engineering based on the organic molecules can be applied to the design and manufacture of electrocatalysts in the field of energy conversion and storage.