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Self-supported transition-metal single-atom catalysts (SACs) facilitate the industrialization of electrochemical CO2 reduction, but suffer from high structural heterogeneity with limited catalytic selectivity. Here we present a facile and scalable approach for the synthesis of self-supported nickel@nitrogen-doped carbon nanotubes grown on carbon nanofiber membrane (Ni@NCNTs/CFM), where the Ni single atoms and nanoparticles (NPs) are anchored on the wall and inside of nitrogen-doped carbon nanotubes respectively. The side effect of Ni NPs was further effectively inhibited by alloying Ni with Cu atoms to alter their d-band center, which is theoretically predicted and experimentally proved. The optimal catalyst Ni9Cu1@NCNTs/CFM exhibits an ultrahigh CO Faradic efficiency over 97% at −0.7 V versus reversible hydrogen electrode. Additionally, this catalyst shows excellent mechanical strength which can be directly used as a self-supporting catalyst for Zn-CO2 battery with a peak power density of ∼0.65 mW/cm2 at 2.25 mA/cm2 and a long-term stability for 150 cycles. This work opens up a general avenue to facilely prepare self-supported SACs with unitary single-atom site for CO2 utilization.

For high-efficiency NH3 synthesis via ambient-condition electrohydrogenation of inert N2, it is pivotal to ingeniously design an active electrocatalyst with multiple features of abundant surfacial deficiency, good conductivity and large surface area. Here, oxygen-deficient SnO2 nanoparticles encapsulated by ultrathin carbon layer (d-SnO2@C) are developed by hydrothermal deposition coupled with annealing process, as promising catalysts for ambient electrocatalytic N2 reduction. d-SnO2@C exhibits high activity and excellent selectivity for electrocatalytic conversion of N2 to NH3 in acidic electrolytes, with Faradic efficiency as high as 12.7% at −0.15 V versus the reversible hydrogen electrode (RHE) and large NH3 yield rate of 16.68 μg h−1 mgcat−1 at −0.25 V vs. RHE in 0.1 M HCl. Benefiting from the structural superiority of enhanced charge transfer efficiency and optimized surface states, d-SnO2@C also achieves excellent long-term stability.

Single metal atoms immobilized on a carbon substrate are of great potential for enhancing the catalytic activities for oxygen reduction and methanol oxidation reactions (ORR/MOR) owing to the maximized atom utilization. Herein, single copper atoms (SCAs) are loaded on macro-porous nitrogen-doped carbon (Cu-NC) derived from zeolitic imidazolate framework-8 (ZIF-8), which are used as catalysts for ORR and Pt-supports for MOR. For ORR, the catalyst marked as Cu-NC-3 exhibits a higher peak potential of 0.87 V (vs. Reversible hydrogen electrode) than that of commercial Pt/C (0.83 V), mainly attributing to that the 3D macro-porous structure of Cu-NC-3 provides adequate space for uniform dispersion of SCAs as the main active species, and smooth diffusion pathways for fast transport of substances (O2, H2O), therefore reducing the overpotential and the intermediate (H2O2) generation to enhance ORR activity. For MOR, Pt-Cu-NC-3 has a higher mass activity of 1217.4 mA/mgPt than that of Pt/C (752.4 mA/mgPt), and its activity maintenance (decline of 27.6%) is also better than Pt/C (decline of 44.0%) after 5000 cyclic voltammetry (CV) cycles. The interactions between SCAs and Pt nanoparticles should facilitate the generation of OH− from water molecules, which can fast eliminate the adsorbed CO to recover the Pt active sites to improve MOR performance. This synthesis strategy affords a new inspiration to prepare single metal atoms loaded on ZIFs-derived macro-structure with diverse activities for ORR/MOR.

Inspired by the relatively recognized performance of transition metal sulfides in the oxidation of hydrazine, the catalytic properties of FeS2 and Fe3S4 are compared via the density functional theory calculations. Due to the different coordination numbers of iron-sulfur, the free energies of the dehydrogenation steps on FeS2 are far less than those on Fe3S4, which led to the much better catalytic performance of FeS2. Accordingly, FeS2 microspheres are rationally proposed as a more efficient electrocatalyst for hydrazine oxidation, which is then prepared by a facile one-step hydrothermal strategy. Such FeS2 microspheres show great activity for hydrazine oxidation with an onset oxidation potential of 0.22 V vs. reversible hydrogen electrode, and a peak current density of 16 mA cm−2. Meanwhile, stability and high faradaic efficiency (3.5e−/N2H4) is obtained for hydrazine oxidation to N2.

Electrochemical nitrogen reduction reaction (NRR) has been identified as a prospective alternative for sustainable ammonia production. Developing cost-effective and highly efficient electrocatalysts is critical for NRR under ambient conditions. Herein, the hierarchical cobalt-molybdenum bimetallic sulfide (CoS2/MoS2) flower-like heterostructure assembled from well-aligned nanosheets has been easily fabricated through a one-step strategy. The efficient synergy between different components and the formation of heterostructure in CoS2/MoS2 nanosheets with abundant active sites makes the non-noble metal catalyst CoS2/MoS2 highly effective in NRR, with a high NH3 yield rate (38.61 μg h–1 mgcat.–1), Faradaic efficiency (34.66%), high selectivity (no formation of hydrazine) and excellent long-term stability in 1.0 mol L–1 K2SO4 electrolyte (pH=3.5) at − 0.25 V versus the reversible hydrogen electrode (vs. RHE) under ambient conditions, exceeding much recently reported cobalt- and molybdenum--based materials, even catch up with some noble-metal-based catalyst. Density functional theory (DFT) calculation indicates that the formation of N2H* species on CoS2(200)/MoS2(002) is the rate-determining step via both the alternating and distal pathways with the maximum ΔG values (1.35 eV). These results open up opportunities for the development of efficient non-precious bimetal-based catalysts for NRR.

Electrochemical CO2 reduction (ECR) powered by renewable energy sources provides a sustainable avenue to producing carbon-neutral fuels and chemicals. The design and development of high performance, cost-effective, and stable catalysts for ECR remain a focus of intense research. Here, we report a novel electrocatalyst, two-dimensional cadmium-based 1,4-benzenedicarboxylate metal-organic frameworks (Cd-BDC MOFs) which can effectively convert CO2 to CO with a faradaic efficiency (FE) of more than 80.0% over the voltage range between −0.9 and −1.1 V (versus reversible hydrogen electrode, vs. RHE) in 0.1 mol·L−1 CO2-saturated KHCO3 solution with an H-type cell, reaching up to 88.9% at −1.0 V (vs. RHE). The performance outperforms commercial CdO and many other MOF-based materials demonstrated in prior literature. The catalytic property can be readily tuned by manipulating synthesis conditions as well as electrolyte type. Especially, high CO FEs exceeding 90.0% can be attained on the Cd-BDC electrode at potentials ranging from −0.16 to −1.06 V (vs. RHE) in 0.5 mol·L−1 KHCO3 solution by using a gas diffusion electrode cell system. The maximum CO FE approaches ∼97.6% at −0.26 V (vs. RHE) and the CO partial geometric current density is as high as about 108.1 mA cm–2 at −1.1 V (vs. RHE). This work offers an efficient, low cost, and alternative electrocatalyst for CO2 transformation.

The development of non-precious based oxygen reduction reaction (ORR) catalysts with outstanding catalytic performance is desirable but still a grand challenge for practical Al-air battery. Herein, we report a vulcanization-assisted pyrolysis strategy for creating zeolitic imidazolate framework-derived catalysts with a N, S co-doped carbon support and highly exposed ZnS and Zn-Nx sites. The trithiocyanuric acid (TCA) is found not only to introduce S into the carbon derived from ZIF-8 and ZnS to adjust the electronic structure of carbon matrix during the pyrolysis, but also result in a shrinkage of carbon framework with a hierarchical porous structure. Such an architecture boosts abundant active sites exposed and accelerates remote mass transportation. As a result, the optimized 3.5ZnS/NSC-NaCl-900 delivers an impressive enhanced performance toward ORR in alkaline medium with a high half-wave potential of 0.905 V (vs. reversible hydrogen electrode), which is superior to most of non-precious metal-based catalysts. Density functional theory calculations unveil that the ZnS in 3.5ZnS/NSC-NaCl-900 can effectively lower the Gibbs energy barrier of crucial steps and therefore promotes the reaction kinetics. Furthermore, 3.5ZnS/NSC-NaCl-900 also displays greater power density and specific capacity than Pt/C in Al-air batteries.

Heteroatom-doped carbon materials have demonstrated great potential in the electrochemical reduction reaction of CO2 (CO2RR) due to their versatile structure and function. However, rational structure control remains one challenge. In this work, we reported a unique carbon precursor of soft template-containing porous poly(ionic liquid) (PIL) that was directly synthesized via free-radical self-polymerization of ionic liquid monomer in a soft template route. Variation of the carbonization temperature in a direct pyrolysis process without any additive yielded a series of carbon materials with facile adjustable textural properties and N species. Significantly, the integration of soft-template in the PIL precursor led to the formation of hierarchical porous carbon material with a higher surface area and larger pore size than that from the template-free precursor. In CO2RR to CO, the champion catalyst gave a Faraday efficiency of 83.0% and a current density of 1.79 mA cm−2 at −0.9 V vs. reversible hydrogen electrode (vs. RHE). The abundant graphite N species and hierarchical pore structure, especially the unique hierarchical small-/ultra-micropores were revealed to enable better CO2RR performance.

Electrocatalytic N2 reduction reaction (NRR) provides a promising route for NH3 production under ambient conditions to replace traditional Haber-Bosch process. For this purpose, efficient NRR electrocatalysts with high NH3 yield rate and high Faradaic efficiency (FE) are required. Cu-based materials have been recognized catalytic active for some multi-electron-involved reduction reactions and usually exhibit inferior catalytic activities for hydrogen evolution reaction. We report here the preparation and characterization of a series of Cu-based nanowires array (NA) catalysts in situ grown on Cu foam (CF) substrate, including Cu(OH)2 NA/CF, Cu3N NA/CF, Cu3P NA/CF, CuO NA/CF and Cu NA/CF, which are directly used as self-supported catalytic electrodes for NRR. The electrochemical results show that CuO NA/CF achieves a highest NH3 yield rate of 1.84 × 10−9 mol s−1 cm−2, whereas Cu NA/CF possesses a highest FE of 18.2% for NH3 production at -0.1 V versus reversible hydrogen electrode in 0.1 M Na2SO4. Such catalytic performances are superior to most of recently reported metal-based NRR electrocatalysts. The contact angle measurements and the simulated calculations are carried out to reveal the important role of the superaerophobic NA surface structure for efficient NRR electrocatalysis.

It is still a great challenge to achieve electrocatalysts for CO2 reduction with high product selectivity and energy conversion efficiency. In this work, Bi nanoparticles supported on polymeric carbon nitride (Bi/CN) have been prepared for CO2 electrocatalytic conversion. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analyses confirm the existence of Bi2O3 on Bi particle surface, forming Bi/Bi2O3 nanoparticles. CN, as the support, has been found not only to improve the dispersibility of Bi/Bi2O3 nanoparticles, but also to enhance the CO2 adsorption on Bi/CN surface owing to the existence of amino and cyano groups. The electronic structure of Bi/CN has been optimized by the interaction between CN and Bi: the electron transfer from Bi to CN results in electron-deficient Bi sites which stabilize CO2-, HCOO- intermediates and accelerate the formation rate of HCOOH. As a result, the maximum Faradaic efficiency of HCOOH reaches 98% at -1.3 to -1.5 V versus reversible hydrogen electrode (vs. RHE) and remains over 91% in a wide potential window of about 500 mV (-1.1 ∼ -1.6 V vs. RHE). The as-obtained Bi/CN in this work shows superior performance to most of the previously reported Bi-based electrocatalysts.

Ammonia (NH3) plays an important role in agriculture and industry. The industry-scale production mainly depends on the Haber-Bosch process suffering from issues of environment pollution and energy consumption. Electrochemical reduction can degrade nitrite (NO2–) pollutants in the environment and convert it into more valuable NH3. Here, Ni2P nanosheet array on nickel foam is proposed as a 3D electrocatalyst for high-efficiency electrohydrogenation of NO2– to NH3 under ambient reaction conditions. When tested in 0.1 M phosphate buffer saline with 200 ppm NO2–, such Ni2P/NF is able to obtain a large NH3 yield rate of 2692.2 ± 92.1 μg h−1 cm−2 (3282.9 ± 112.3 μg h−1 mgcat.−1), a high Faradic efficiency of 90.2 ± 3.0%, and selectivity of 87.0 ± 1.7% at −0.3 V versus a reversible hydrogen electrode. After 10 h of electrocatalytic reduction, the conversion rate of NO2– achieves near 100%. The catalytic mechanism is further investigated by density functional theory calculations.

We have developed an efficient strategy to synthesize an active and durable electrocatalyst of Pd hydride nanocubes (NCs). Instead of the traditional chemical method, the PdH0.43 NCs are firstly prepared via a hydrogen diffusion procedure, followed by hydrothermal synthesis of an amorphous CuO layer encapsulating the PdH0.43 NCs to prevent the hydrogen atoms from escaping. Obvious lattice expansion is demonstrated playing a pivotal role in the enhancement of their oxygen reduction reaction (ORR) activity and durability. The obtained PdH0.43@CuO NCs catalysts exhibit an ORR mass activity of 0.18 A mg−1 at 0.90 V versus reversible hydrogen electrode in an alkaline medium, which is about five times higher than that of commercial Pt/C. Accelerated durability tests show that there is only a 32 mV decay in half-wave potential even after 10,000 potential cycles, indicating the excellent stability of PdH0.43@CuO NCs. Density functional theory (DFT) calculations also indicate that, compared to Pd, PdH0.43 has a lower limiting barrier to form OH− during the ORR process. The present study illustrates the importance of lattice expansion caused by hydrogen and offers an available strategy to design highly efficient and durable Pd-based electrocatalysts for alkaline fuel cells.

A peerless inexpensive electrochemical engineering of spherical Pt nanoparticles (nano-Pt: ca. 100 nm in average diameter) was achieved with intersected ferric oxyhydroxide nanotubes (α-FeOOH (goethite): ca. 20 nm in average diameter). The FeOOH@Pt catalyst exhibited ca. 2.5 and 1.94-times increases in the catalytic activity and poisoning tolerance, respectively, of the formic acid electro−oxidation (FAO) – the anodic reaction in the direct formic acid fuel cells (DFAFCs). Surprisingly, with a post-activation of the FeOOH@Pt catalyst at 0.48 V vs. reversible hydrogen electrode (RHE) in 0.2 mol L−1 NaOH, a favorable Fe2+/Fe3+ transformation succeeded to eliminate the permanent CO poisoning of Pt that impaired the catalytic performance of DFAFCs. This was synchronized (relatively to nano-Pt) with a four-fold increase in the catalytic efficiency, ca. −174 mV shift in the onset potential, and eightfold enhancement in the catalyst's durability for FAO. The activated FeOOH@Pt catalyst also showed a mass activity of 296 mA mg−1Pt (at 0.8 V), which was ca. nine times higher than that (34 mA mg−1Pt) of the commercial Pt/C catalyst. The ascertained improvement in the electron transfer at the FeOOH@Pt surface foresees quick industrialization for DFAFCs.

Sustainable hydrogen gas production is critical for future fuel infrastructure. Here, a series of phosphorous-doped carbon nitride materials were synthesized by thermal annealing of urea and ammonium hexafluorophosphate, and platinum was atomically dispersed within the structural scaffold by thermal refluxing with Zeise's salt forming Pt–N/P/Cl coordination interactions, as manifested in X-ray photoelectron and absorption spectroscopic measurements. The resulting materials were found to exhibit markedly enhanced electrocatalytic activity towards the hydrogen evolution reaction (HER) in acidic media, as compared to the P-free counterpart. This was accounted for by P doping that led to a significantly improved charge carrier density within C3N4, and the sample with the optimal P content showed an overpotential of only −22 mV to reach the current density of 10 mA cm−2, lower than that of commercial Pt/C (−26 mV), and a mass activity (7.1 mA μg−1Pt at −70 mV vs. reversible hydrogen electrode) nearly triple that of the latter. Results from the present study highlight the significance of P doping in the manipulation of the electronic structures of metal/carbon nitride nanocomposites for high-performance HER electrocatalysis.

Metal-N4 (M-N4) macrocyclic complexes are interesting electrocatalysts due to their well-defined structures and rich molecular tuning. Among them, metal phthalocyanines have been widely studied for the carbon dioxide reduction reaction (CO2RR) in heterogeneous systems and demonstrated good electrocatalytic performance. However, other complexes like metal corroles and metal porphyrins are much less explored, and often show inferior performances. In this study, three cobalt macrocyclic complexes, cobalt phthalocyanine, cobalt meso-tetraphenylporphyrin, and cobalt meso-triphenylcorrole (CoPc, CoTPP and CoTPC) are investigated in heterogeneous electrocatalysis of CO2RR. Although CoPc/carbon nanotube (CNT) hybrid exhibits high electrocatalytic activity, CNT hybridization does not work for CoTPC and CoTPP that hold weak interactions with CNTs. By the drop-dry method with a high molecular loading of 5.4 × 10–7 mol cm–2, CoTPC and CoTPP could deliver appreciable electrode activities. Poly(4-vinylpyridine) (PVP) introduction is further demonstrated as a facile method to afford enhanced activities for CoTPP at low molecular loadings through enhancing molecule-substrate interactions. The partial current density of carbon monoxide for CoTPP+CNT/PVP is around 8 times higher than the sample without PVP at –0.67 V versus reversible hydrogen electrode. This work provides solutions to enhance the electrode activities of molecular electrocatalysts with weak substrate interactions in heterogeneous systems.

Tantalum nitride (Ta3N5) is a very promising photoanode material due to its narrow band gap (2.1 eV) and suitable band alignment for solar water splitting. However, it suffers from severe photocorrosion during water oxidation. In this work, it was found that surface passivation by AlOx and TiOx layers results in dramatically different PEC performance of Ta3N5 photoanode for water oxidation. The mechanism study indicates that the negative charges on AlOx can generate additional field to promote separation of photogenerated charges, while the positive charges on TiOx layer show the opposite effect. As a result, the Ta3N5 based photoanode modified with AlOx layer gives a high photocurrent of 12.5 mA cm−2 for 24 h at 1.23 V versus the reversible hydrogen electrode (RHE). Dynamic analysis implies that the hole extraction and transfer are significantly improved by the modification with the AlOx layer. This work reveals the importance of the charges on surface passivation layer in interface engineering of photoelectrodes.

In pursuit of environmental friendliness and high economic efficiency, renewable energy-driven selective acetylene semihydrogenation under ambient conditions is urgently requisite but remain a grand challenge. Herein, we explore single-atom nickel (Ni) dispersed N-doped carbon (SA-Ni-NC) as novel electrocatalysts for catalyzing selective acetylene semihydrogenation. In-situ electrochemical Raman and theoretical investigations reveal that weak π-adsorption of ethylene on individual Ni sites in SA-Ni-NC facilitates its desorption and thus avoids its overhydrogenation. Eventually, under pure acetylene flow, SA-Ni-NC exhibits a high ethylene Faradaic efficiency (FEethylene) of 91.3 %, and a large current density of −92.2 mA cm−2 at −0.6 V vs. reversible hydrogen electrode (RHE). Even in crude ethylene stream containing 1 % acetylene impurities (1×104 ppm), SA-Ni-NC still manifest a high acetylene conversion of 97.4 % with a large space velocity (SV) of 2.4×104 mL gcat–1 h–1 and a high turnover frequency (TOF) of 22.9 h−1 for each Ni atom.

Summary Electrochemical water splitting provides a green pathway for hydrogen generation, while iridium oxide (IrO2) is almost the only stable anode catalyst for acidic media. Yet, it is still a huge challenge to develop an efficient IrO2 catalyst. Here, we demonstrate a microwave-assisted mechano-thermal method that achieves a new 3R phase IrO2. This 3R-IrO2 achieves an ultralow overpotential of 188 mV at the current density of 10 mA cmgeo−2 and a notably high turnover frequency of 5.7 sUPD−1 at 1.50 V versus reversible hydrogen electrode. It also endures limited decay under the current density of 10 mA cmgeo−2 for 511 h prolong test in acidic electrolyte. The new active sites of the edge-sharing structure in 3R-IrO2 and the fast proton transportation along interlayers and intralayers through iridium vacancies contribute to the extraordinary acidic oxygen evolution reaction (OER) activity and stability. This work highlights the great potential of new metastable materials toward advanced electrocatalysis.

Extensive research to explore cost-effective carbon materials as electrocatalysts and electrode materials for energy conversion and storage has been conducted in the recent literature. This raised a crucial question regarding the origin of this electrocatalytic activity from the heteroatom doping/ hierarchical porous defect-rich architecture and/ or the trace metal impurities introduced during synthesis/ inherent to the precursor. In this work, an insight into this issue is provided by considering a lignocellulosic biowaste, Euryale Ferox (foxnut) shells as a precursor to derive micro/ mesoporous defective graphitic carbon sheets by the phosphoric acid (H3PO4) dictated in-situ carbonization for oxygen reduction reaction (ORR) and supercapacitor applications. The sample synthesized at 900 °C (FP900) shows an onset potential of 0.98 V vs. reversible hydrogen electrode (RHE), ORR current density of 5.5 mA cm−2, and current stability of 93% (in 10 h measurement) in 0.1 M KOH. In addition, a symmetric supercapacitor device is assembled using the prepared material and the specific capacitance of 207.5 F g−1 at 1 A g−1 is obtained. An attempt to explain the origin of the electrochemical performance is made by establishing parallels with the physicochemical characterizations. The inherently doped heteroatoms give rise to electroactive functionalities and the wide enough pore size distribution improves the active sites utilization efficiency by enhancing the accessibility to electrolytic ions resulting in better electrochemical performance. Furthermore, the contribution from the intrinsic trace metal impurities is evaluated using X-ray fluorescence (XRF) spectroscopy. The presented research clarifies the non-contributing nature of trace metal species owing to the inaccessibility of active sites and lower abundance in F900 and FP900, respectively.

Due to the serious recombination of electron-hole and weak photoresponse ability, achieving highly efficient photoelectrochemical (PEC) water splitting activity for TiO2 photoelectrode has become a key issue. In this paper, we reported a new method for preparing ZnO/TiO2 photoelectrodes by electrostatic adsorption from zeolitic imidazolate framework-8 (ZIF-8) as the precursor. ZIF-8 was combined with TiO2 nanorods (NRs) through electrostatic interaction and then calcined to obtain ZnO/TiO2 heterojunction photoelectrodes with abundant oxygen vacancies (Ovac). The introduced ZnO with Ovac provides a large number of active sites which enhanced the electrical conductivity and charges separation of ZnO/TiO2 photoelectrode. The optimal photocurrent density of ZnO/TiO2 photoelectrodes at 1.23 V versus (vs.) reversible hydrogen electrode (RHE) under illumination (100 mW/cm2) has reached 1.76 mA/cm2, almost 2.75 times that of the pure TiO2. Meanwhile, the incident photon-to-electron conversion efficiency (IPCE) of the best photoelectrode has increased to 58.2% at 390 nm, the charge injection (ηinjection) and separation (ηseparation) efficiency have reached to 93.53% and 51.62% (1.23 V vs. RHE), respectively.

The long-term stability in acidic or alkaline aqueous electrolytes of p-Ga0.52In0.48P photocathodes, with a band gap of ∼1.8 eV, for the solar-driven hydrogen-evolution reaction (HER) has been evaluated from a thermodynamic, kinetic, and mechanistic perspective. At either pH 0 or pH 14, etched p-GaInP electrodes corroded cathodically under illumination and formed metallic In0 on the photoelectrode surface. In contrast, under the same conditions, electrodeposition of Pt facilitated the HER kinetics and stabilized p-GaInP/Pt photoelectrodes against such cathodic decomposition. When held at 0 V versus the reversible hydrogen electrode, p-GaInP/Pt electrodes in either pH = 0 or pH = 14 exhibited stable current densities (J) of ∼-9 mA cm-2 for hundreds of hours under simulated 1 sun illumination. During the stability tests, the current density-potential (J-E) characteristics of the p-GaInP/Pt photoelectrodes degraded due to pH-dependent changes in the surface chemistry of the photocathode. This work provides a fundamental understanding of the stability and corrosion mechanisms of p-GaInP photocathodes that constitute a promising top light absorber for tandem solar-fuel generators.

Electrochemical nitrogen reduction reaction (NRR) under ambient conditions is highly desirable to achieve sustainable ammonia (NH3) production via an alternative carbon free strategy. Single-atom catalysts (SACs) with super high atomic utilization and catalytic efficiency exhibit great potential for NRR. Herein, a high-performance NRR SAC is facilely prepared via a simple deposition method to anchor Au single atoms onto porous β-FeOOH nanotubes. The resulting Au-SA/FeOOH can efficiently drive NRR under ambient conditions, and the NH3 yield reaches as high as 2,860 µg·h−1·mgAu−1 at −0.4 V vs. reversible hydrogen electrode (RHE) with 14.2% faradaic efficiency, much superior to those of all the reported Au-based electrocatalysts. Systematic investigations demonstrate that the synergy of much enhanced N2 adsorption, directional electron export, and mass transfer ability in Au-SA/FeOOH greatly contributes to the superior NRR activity. This work highlights a new insight into the design of high efficient NRR electrocatalysts by combination of porous metal oxide matrix and highly active single-atom sites.

Modulation of A-site defects is crucial to the redox reactions on ABO3 perovskites for both clean air application and electrochemical energy storage. Herein we report a scalable one-pot strategy for in situ regulation of La vacancies (V La) in LaMnO3.15 by simply introducing urea in the traditional citrate process, and further reveal the fundamental relationship between V La creation and surface lattice oxygen (Olatt ) activation. The underlying mechanism is shortened Mn-O bonds, decreased orbital ordering, promoted MnO6 bending vibration and weakened Jahn-Teller distortion, ultimately realizing enhanced Mn-3d and O-2p orbital hybridization. The LaMnO3.15 with optimized V La exhibits order of magnitude increase in toluene oxidation and ~0.05 V versus RHE (reversible hydrogen electrode) increase of half-wave potential in oxygen reduction reaction (ORR). The reported simple but effective strategy for in situ modulation of La-site defects and the corresponding influence on the electronic structure of MnO6 can benefit the development of novel defect-meditated perovskites in both heterocatalysis and electrocatalysis.

Direct photoelectrochemical (PEC) water splitting is a promising solution for solar energy conversion; however, there is a pressing bottleneck to address the intrinsic charge transport for the enhancement of PEC performance. Herein, a versatile coupling strategy was developed to engineer atomically dispersed Ni-N4 sites coordinated with an axial direction oxygen atom (Ni-N4-O) incorporated between oxygen evolution cocatalyst (OEC) and semiconductor photoanode, boosting the photogenerated electron-hole separation and thus improving PEC activity. This state-of-the-art OEC/Ni-N4-O/BiVO4 photoanode exhibits a record high photocurrent density of 6.0 mA cm-2 at 1.23 V versus reversible hydrogen electrode (vs RHE), over approximately 3.97 times larger than that of BiVO4, achieving outstanding long-term photostability. From X-ray absorption fine structure analysis and density functional theory calculations, the enhanced PEC performance is attributed to the construction of single-atomic Ni-N4-O moiety in OEC/BiVO4, facilitating the holes transfer, decreasing the free energy barriers, and accelerating the reaction kinetics. This work enables us to develop an effective pathway to design and fabricate efficient and stable photoanodes for feasible PEC water splitting application.

The electrochemical N2 reduction reaction (NRR) under ambient conditions is attractive in replacing the current Haber-Bosch process toward sustainable ammonia production. Metal-heteroatom-doped carbon-rich materials have emerged as the most promising NRR electrocatalysts. However, simultaneously boosting their NRR activity and selectivity remains a grand challenge, while the principle for precisely tailoring the active sites has been elusive. Herein, we report the first case of crystalline two-dimensional conjugated covalent organic frameworks (2D c-COFs) incorporated with M–N4–C centers as novel, defined, and effective catalysts, achieving simultaneously enhanced activity and selectivity of electrocatalytic NRR to ammonia. Such 2D c-COFs are synthesized based on metal-phthalocyanine (M = Fe, Co, Ni, Mn, Zn, and Cu) and pyrene units bonded by pyrazine linkages. Significantly, the 2D c-COFs with Fe–N4–C center exhibit higher ammonia yield rate (33.6 μg h–1 mgcat–1) and Faradaic efficiency (FE, 31.9%) at −0.1 V vs reversible hydrogen electrode than those with other M–N4–C centers, making them among the best NRR electrocatalysts (yield rate >30 μg h–1 mgcat–1 and FE > 30%). In situ X-ray absorption spectroscopy, Raman spectroelectrochemistry, and theoretical calculations unveil that Fe–N4–C centers act as catalytic sites. They show a unique electronic structure with localized electronic states at Fermi level, allowing for stronger interaction with N2 and thus faster N2 activation and NRR kinetics than other M–N4–C centers. Our work opens the possibility of developing metal–nitrogen-doped carbon-rich 2D c-COFs as superior NRR electrocatalyst and provides an atomic understanding of the NRR process on M–Nx–C based electrocatalysts for designing high-performance NRR catalysts.

Development of efficient bifunctional nonprecious metallic electrocatalysts for hydrogen electrochemistry in alkaline solution is of importance to enable commercialization of a low-cost alkaline hydrogen fuel cell and water electrolyzer, but it is very challenging. Two-dimensional (2D) MXene-based electrocatalysts hold tremendous potential for the applications of hydrogen fuel cell and water electrolyzer. Here, we successfully immobilized transition-metal-based NiMo nanoparticles (NPs) on 2D Ti3C2Tx (Tx: surface terminations, such as O, OH, or F) surfaces by a wet chemical method. Our results demonstrate that the NiMo NPs are monodispersed on Ti3C2Tx with surface functionalization. These monodisperse NPs resulted in superior hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR) activities in an alkaline media. The NiMo NPs/Ti3C2Tx in 1.0 M KOH yielded an HER current of -10 mA cm-2 at -0.044 V vs reversible hydrogen electrode (RHE), nearly 232 mV smaller than that of the parent NiMo NPs. The NiMo NPs/Ti3C2Tx produced an HOR current density of 1.5 mA cm-2 at 0.1 V vs RHE. Density functional theory (DFT) results further reveal that Ti3C2Tx support can facilitate the charge transfer to metallic NPs and tailor the electronic structure of catalytic sites, resulting in optimized adsorption free energies of H* species for hydrogen electrochemistry. This work provides a facile and universal strategy in the development of 2D Ti3C2Tx with nonprecious metals for low-cost bifunctional hydrogen electrocatalysts.

Production of multicarbon (C2+ ) liquid fuels is a challenging task for electrocatalytic CO2 reduction, mainly limited by the stabilization of reaction intermediates and their subsequent C-C couplings. In this work, we report a unique catalyst, the coordinatively unsaturated Cu sites on amorphous CuTi alloy (a-CuTi@Cu) toward electrocatalytic CO2 reduction to multicarbon (C2-4 ) liquid fuels. Remarkably, the electrocatalyst yields ethanol, acetone, and n-butanol as major products with a total C2-4 faradaic efficiency of about 49 % at -0.8 V vs. reversible hydrogen electrode (RHE), which can be maintained for at least 3 months. Theoretical simulations and in situ characterization reveals that subsurface Ti atoms can increase the electron density of surface Cu sites and enhance the adsorption of *CO intermediate, which in turn reduces the energy barriers required for *CO dimerization and trimerization.

Highly efficient catalysts with enough selectivity and stability are essential for electrochemical nitrogen reduction reaction (e-NRR) that has been considered as a green and sustainable route for synthesis of NH3. In this work, a series of three-dimensional (3D) porous iron foam (abbreviated as IF) self-supported FeS2-MoS2 bimetallic hybrid materials, denoted as FeS2-MoS2@IFx, x = 100, 200, 300, and 400, were designed and synthesized and then directly used as the electrode for the NRR. Interestingly, the IF serving as a slow-releasing iron source together with polyoxomolybdates (NH4)6Mo7O24·4H2O as a Mo source were sulfurized in the presence of thiourea to form self-supported FeS2-MoS2 on IF (abbreviated as FeS2-MoS2@IF200) as an efficient electrocatalyst. Further material characterizations of FeS2-MoS2@IF200 show that flower cluster-like FeS2-MoS2 grows on the 3D skeleton of IF, consisting of interconnected and staggered nanosheets with mesoporous structures. The unique 3D porous structure of FeS2-MoS2@IF together with synergy and interface interactions of bimetallic sulfides would make FeS2-MoS2@IF possess favorable electron transfer tunnels and expose abundant intrinsic active sites in the e-NRR. It is confirmed that synthesized FeS2-MoS2@IF200 shows a remarkable NH3 production rate of 7.1 ×10-10 mol s-1 cm-2 at -0.5 V versus the reversible hydrogen electrode (vs RHE) and an optimal faradaic efficiency of 4.6% at -0.3 V (vs RHE) with outstanding electrochemical and structural stability.

The Sn electrode possesses a high selectivity for formate production in electrochemical CO2 reduction. Understanding the relationship between the selectivity of formate and surface characteristics such as structure and chemical state is important for obtaining high activity. In this study, we fabricated a porous Sn electrode using a simple method of anodization in lactic acid. The anodized electrode had numerous 1-μm pores and its surface chemical state had a relatively high ratio of Sn0 compared with that of a bare Sn electrode. In the CO2 reduction reaction, the anodized Sn electrode showed a Faradaic efficiency (FE) of 35% for formate production at a low applied potential of −0.6 V vs. a reversible hydrogen electrode (RHE), with suppressed H2 generation. A Tafel analysis revealed that the slope of the anodized Sn electrode was 70 mV/decade, suggesting an increase in the stability of the CO2 radical anion. These results indicated that a coordinative unsaturation site such as the edge site formed by anodization contributes to a decrease in the overpotential and an increase in the reactive sites for formate production. Moreover, the surface structure appeared to be a significant factor in the production of formate at a very low applied potential relative to the surface oxidation state. The porous Sn electrode was prepared by anodization in lactic acid to increase the selectivity for formate at a low applied potential. Prepared porous Sn electrode enhances formate production from the CO2RR at a low applied potential due to the stabilization of the CO2 or its reaction intermediates.

Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is still seriously impeded by the inferior NH3 yield and low Faradaic efficiency, especially at low overpotentials. Herein, we report the synthesis of nano-sized RuO2 and Bi2 O3 particles grown on functionalized exfoliated graphene (FEG) through in situ electrodeposition, denoted as RuO2 -Bi2 O3 /FEG. The prepared self-supporting RuO2 -Bi2 O3 /FEG hybrid with a Bi mass loading of 0.70 wt% and Ru mass loading of 0.04 wt% shows excellent NRR performance at low overpotentials in acidic, neutral and alkaline electrolytes. It achieves a large NH3 yield of 4.58±0.16 μgNH3 h-1 cm-2 with a high Faradaic efficiency of 14.6 % at -0.2 V versus reversible hydrogen electrode in 0.1 M Na2 SO4 electrolyte. This performance benefits from the synergistic effect between Bi2 O3 and RuO2 which respectively have a fairly strong interaction of Bi 6p orbitals with the N 2p band and abundant supply of *H, as well as the binder-free characteristic and the convenient electron transfer via graphene nanosheets. This work highlights a new electrocatalyst design strategy that combines transition and main-group metal elements, which may provide some inspirations for designing low-cost and high-performance NRR electrocatalysts in the future.

Design of efficient catalysts for electrochemical reduction of carbon dioxide (CO2) with high selectivity and activity is of great challenge, but significant for managing the global carbon balance. Herein, a series of three-dimensional (3D) single-atom metals anchored on graphene networks (3D SAM-G) with open-pore structure were successfully mass-produced via a facile in-situ calcination technique assisted by NaCl template. As-obtained 3D SANi-G electrode delivers excellent CO Faradaic efficiency (FE) of >96% in the potential range of −0.6 to −0.9 V versus reversible hydrogen electrode (RHE) and a high current density of 66.27 mA cm−2 at −1.0 V versus RHE, outperforming most of the previously reported catalysts tested in H-type cells. Simulations indicate that enhanced mass transport within the 3D open-pore structure effectively increases the catalytically active sites, which in turn leads to simultaneous enhancement on selectivity and activity of 3D SANi-G toward CO2 electroreduction. The cost-effective synthesis approach together with the microstructure design concept inspires new insights for the development of efficient electrocatalysts.

Developing efficient and stable catalysts for electrochemical CO2 reduction reaction (CO2RR) in a wide potential window is highly desirable for achieving carbon neutrality, but remains greatly challenging. Herein, we demonstrate a facile synthetic strategy to synthesize transition metal nickel-nitrogen-carbon (Ni-N-C) catalyst where nickel nanoparticles have been in-situ encapsulated into N-doped carbon nanotubes (Ni@NCNT) for CO2RR. Strikingly, the as-prepared Ni@NCNT catalyst shows a high CO Faradaic efficiency (>90%) in a wide potential range of −0.65 to −1.0 V versus reversible hydrogen electrode (vs. RHE), a large current density of 16.3 mA cm−2 at −0.8 V vs. RHE and robust durability after a continuous electroreduction of 18 h. Density functional theory calculations suggest that compared to pure Ni (111) and Ni nanoparticles-free solid N-doped carbon nanorods (NCNR), Ni@NCNT can more effectively suppress H2 evolution and stabilize ∗COOH intermediates without influencing ∗CO desorption, thus, giving rise to high activity and desirable selectivity toward CO2RR.

Herein, a newly developed non-noble metal water splitting catalyst based on NiCuCoS3 was reported. Water splitting catalysts are largely developed with noble-based transition metals to lower the energy requirement for the overall water splitting reactions. However, the high cost of precious metal-based catalyst necessitated ongoing search for cheap and efficient oxygen and hydrogen evolution reaction catalysts. NiCuCoS3 were prepared by solventless solid state method and was well characterized by several techniques including field emission scanning electron microscopy (FESEM), X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), Fourier Transform infrared red spectroscopy (FTIR), energy dispersive X-ray spectroscopy (XEDS). The as-prepared NiCuCoS3 was applied for water splitting activities with satisfactory performance. The onset for the oxygen evolution reaction (OER) in 1 M KOH was noticed at the electrode potential E = 1.78 V-/RHE (vs. the reversible hydrogen electrode corresponding to an overpotential eta = 0.55 V, with a current density of 10 mA cm(2) obtained at E = 1.92 V-/RHE (eta = 0.69 V). Similarly, the hydrogen evolution reaction (HER) occurred at an onset of E = 0.58 V-/RHE, with a current density of 10 mA/cm(2) obtained at E = 0.60 V-/RHE (with h equal to E vs. RHE for the HER). Likewise, OER and HER had Tafel slopes (130 mV/dec and 116 mV/dec respectively). The developed catalyst also showed high stability as established by linear sweep voltammetry, chronoamperometry and chronopotentiometry. This approach is seen as the right track of making water electrolysis for hydrogen energy feasible through provision of low-energy requirement for electrolytic process. (C) 2021 The Author(s). Published by Elsevier B.V.

Herein, an effective tandem catalysis strategy is developed to improve the selectivity of the CO2 RR towards C2 H4 by multiple distinct catalytic sites in local vicinity. An earth-abundant elements-based tandem electrocatalyst PTF(Ni)/Cu is constructed by uniformly dispersing Cu nanoparticles (NPs) on the porphyrinic triazine framework anchored with atomically isolated nickel-nitrogen sites (PTF(Ni)) for the enhanced CO2 RR to produce C2 H4 . The Faradaic efficiency of C2 H4 reaches 57.3 % at -1.1 V versus the reversible hydrogen electrode (RHE), which is about 6 times higher than the non-tandem catalyst PTF/Cu, which produces CH4 as the major carbon product. The operando infrared spectroscopy and theoretic density functional theory (DFT) calculations reveal that the local high concentration of CO generated by PTF(Ni) sites can facilitate the C-C coupling to form C2 H4 on the nearby Cu NP sites. The work offers an effective avenue to design electrocatalysts for the highly selective CO2 RR to produce multicarbon products via a tandem route.

Vertical Si nanowire (NW) arrays are a promising photoanode material in the photoelectrochemical (PEC) water splitting field because of their highly efficient light absorption capability and large surface areas for PEC reactions. However, Si NW arrays always suffer from high overpotential, low photocurrent density, and low applied bias photon-to-current efficiency (ABPE) due to their low surface catalytic activity and intense charge recombination. Here, we report an efficient oxygen evolution cocatalyst of optically transparent, mesoporous ultrathin (2.47 nm thick) In2O3 nanosheets, which are coupled on the top of Si NW arrays. Combined with a conformal TiO2 thin film as an intermediate protective layer, this Si NW/TiO2/In2O3 (2.47 nm) heterostructured photoanode exhibited an extremely low onset potential of 0.6 V vs reversible hydrogen electrode (RHE). The Si NW/TiO2/In2O3 (2.47 nm) photoanode also showed a high photocurrent density of 27 mA cm-2 at 1.23 V vs RHE, more than 1 order of magnitude higher than that of the Si NW/TiO2 photoanodes. This improvement in solar water splitting performance was attributed to the significantly promoted charge injection efficiency as a result of the In2O3 nanosheet coupling. This work presents a promising pathway for developing efficient Si-based photoanodes by coupling ultrathin 2D cocatalysts.

The decentralized production of H2O2via a two-electron oxygen reduction reaction (2e− ORR) has emerged as a promising alternative to the energy-intensive anthraquinone (AQ) process. However, its practical application requires 2e− ORR electrocatalysts with high activity and selectivity. Herein, we report the synthesis of metallic Ni nanoparticles anchored on bacterial cellulose-derived carbon fibers (Ni-NPs/BCCF) via a facile impregnation-pyrolysis method as efficient electrocatalysts for 2e− ORR to H2O2. By tuning the amount of Ni precursor, the best electrocatalytic performance toward 2e− ORR was achieved for Ni-NPs/BCCF-20.7, affording a high H2O2 selectivity of ∼90% and an onset potential of 0.75 V vs. reversible hydrogen electrode (RHE) in an alkaline electrolyte. Ni-NPs/BCCF-20.7 achieved the largest H2O2 yield rate of 162.7 ± 13.7 mmol gcat−1 h−1 and the highest Faradaic efficiency of 93.9% ± 4.2% at 0.2 and 0.5 V vs. RHE from the bulk ORR system, respectively. Theoretical calculations revealed the more favorable “end-on” adsorption configuration of molecular oxygen on the exposed Ni(111) plane, which can effectively suppress the O-O bond dissociation, resulting in high selectivity for H2O2 generation.