Deep Electron Redistributions Induced by Dual Junctions Facilitating Electroreduction of Dilute Nitrate to Ammonia.

The electronic states of metal catalysts can be redistributed by the rectifying contact between metal and semiconductor e.g., N-doped carbon (NC), while the interfacial regulation degree is very limited. Herein, a deep electronic state regulation is achieved by constructing a novel double-heterojunctional Co/Co3O4@NC catalyst containing Co/Co3O4 and Co3O4/NC heterojunctions. When used for dilute electrochemical NO3 - reduction reaction (NO3RR), the as-prepared Co/Co3O4@NC exhibits an outstanding Faradaic efficiency for NH3 formation (FENH3) of 97.9%, -0.4 V versus RHE and significant NH3 yield of 303.5 mmol h-1 gcat -1 at -0.6 V at extremely low nitrate concentrations (100 ppm NO3 --N). Experimental and theoretical results reveal that the dual junctions of Co/Co3O4 and Co3O4/NC drive a unidirectional electron transfer from Co to NC (Co→Co3O4→NC), resulting in electron-deficient Co atoms. The electron-deficient Co promotes NO3 - adsorption, the rate-determining step (RDS) for NO3RR, facilitating the dilute NO3RR to NH3. The design strategy provides a novel reference for unidirectional multistage regulation of metal electronic states boosting electrochemical dilute NO3RR, which opens up an avenue for deep electronic state regulation of electrocatalyst breaking the limitation of the electronic regulation degree by rectifying contact.

Boosting Electrochemical Nitrate Reduction at Low Concentrations Through Simultaneous Electronic States Regulation and Proton Provision.

Electrochemically converting nitrate (NO3 -) into ammonia (NH3) has emerged as an alternative strategy for NH3 production and effluent treatment. Nevertheless, the electroreduction of dilute NO3 - is still challenging due to the competitive adsorption between various aqueous species and NO3 -, and unfavorable water dissociation providing *H. Herein, a new tandem strategy is proposed to boost the electrochemical nitrate reduction reaction (NO3RR) performance of Cu nanoparticles supported on single Fe atoms dispersed N-doped carbon (Cu@Fe1-NC) at dilute NO3 - concentrations (≤100 ppm NO3 --N). The optimized Cu@Fe1-NC presents a FENH3 of 97.7% at -0.4 V versus RHE, and a significant NH3 yield of 1953.9 mmol h-1 gCu -1 at 100 ppm NO3 --N, a record-high activity for dilute NO3RR. The metal/carbon heterojunctions in Cu@Fe1-NC enable a spontaneous electron transfer from Cu to carbon substrate, resulting in electron-deficient Cu. As a result, the electron-deficient Cu facilitates the adsorption of NO3 - compared with the pristine Cu. The adjacent atomic Fe sites efficiently promote water dissociation, providing abundant *H for the hydrogenation of *NOx e at Cu sites. The synergistic effects between Cu and single Fe atom sites simultaneously decrease the energy barrier for NO3 - adsorption and hydrogenation, thereby enhancing the overall activity of NO3 - reduction.

Dopant-Induced Electronic States Regulation Boosting Electroreduction of Dilute Nitrate to Ammonium.

Electrochemically converting NO3 - into NH3 offers a promising route for water treatment. Nevertheless, electroreduction of dilute NO3 - is still suffering from low activity and/or selectivity. Herein, B as a modifier was introduced to tune electronic states of Cu and further regulate the performance of electrochemical NO3 - reduction reaction (NO3 RR) with dilute NO3 - concentration (≤100 ppm NO3 - -N). Notably, a linear relationship was established by plotting NH3 yield vs. the oxidation state of Cu, indicating that the increase of Cu+ content leads to an enhanced NO3 - -to-NH3 conversion activity. Under a low NO3 - -N concentration of 100 ppm, the optimal Cu(B) catalyst displays a 100 % NO3 - -to-NH3 conversion at -0.55 to -0.6 V vs. RHE, and a record-high NH3 yield of 309 mmol h-1 gcat -1 , which is more than 25 times compared with the pristine Cu nanoparticles (12 mmol h-1 gcat -1 ). This research provides an effective method for conversion of dilute NO3 - to NH3 , which has certain guiding significance for the efficient and green conversion of wastewater in the future.

A Tandem Strategy for Enhancing Electrochemical CO2 Reduction Activity of Single-Atom Cu-S1 N3 Catalysts via Integration with Cu Nanoclusters.

We developed a tandem electrocatalyst for CO2 -to-CO conversion comprising the single Cu site co-coordinated with N and S anchored carbon matrix (Cu-S1 N3 ) and atomically dispersed Cu clusters (Cux ), denoted as Cu-S1 N3 /Cux . The as-prepared Cu-S1 N3 /Cux composite presents a 100 % Faradaic efficiency towards CO generation (FECO ) at -0.65 V vs. RHE and high FECO over 90 % from -0.55 to -0.75 V, outperforming the analogues with Cu-N4 (FECO only 54 % at -0.7 V) and Cu-S1 N3 (FECO 70 % at -0.7 V) configurations. The unsymmetrical Cu-S1 N3 atomic interface in the carbon basal plane possesses an optimized binding energy for the key intermediate *COOH compared with Cu-N4 site. At the same time, the adjacent Cux effectively promotes the protonation of *CO2 - by accelerating water dissociation and offering *H to the Cu-S1 N3 active sites. This work provides a tandem strategy for facilitating proton-coupled electron transfer over the atomic-level catalytic sites.

Control over Electrochemical Water Oxidation Catalysis by Preorganization of Molecular Ruthenium Catalysts in Self-Assembled Nanospheres.

Oxygen formation through water oxidation catalysis is a key reaction in the context of fuel generation from renewable energies. The number of homogeneous catalysts that catalyze water oxidation at high rate with low overpotential is limited. Ruthenium complexes can be particularly active, especially if they facilitate a dinuclear pathway for oxygen bond formation step. A supramolecular encapsulation strategy is reported that involves preorganization of dilute solutions (10-5 m) of ruthenium complexes to yield high local catalyst concentrations (up to 0.54 m). The preorganization strategy enhances the water oxidation rate by two-orders of magnitude to 125 s-1 , as it facilitates the diffusion-controlled rate-limiting dinuclear coupling step. Moreover, it modulates reaction rates, enabling comprehensive elucidation of electrocatalytic reaction mechanisms.

Highly Efficient Photoelectrochemical Water Splitting with an Immobilized Molecular Co4 O4 Cubane Catalyst.

Molecular Co4 O4 cubane water oxidation catalysts were combined with BiVO4 electrodes for photoelectrochemical (PEC) water splitting. The results show that tuning the substituent groups on cobalt cubane allows the PEC properties of the final molecular catalyst/BiVO4 hybrid photoanodes to be tailored. Upon loading a new cubane complex featuring alkoxy carboxylato bridging ligands (1 h) on BiVO4 , an AM 1.5G photocurrent density of 5 mA cm-2 at 1.23 V vs. RHE for water oxidation was obtained, the highest photocurrent for undoped BiVO4 photoanodes. A high solar-energy conversion efficiency of 1.84 % was obtained for the integrated photoanode, a sixfold enhancement over that of unmodified BiVO4 . These results and the high surface charge separation efficiency support the role of surface-modified molecular catalysts in improving PEC performance and demonstrate the potential of molecule/semiconductor hybrids for efficient artificial photosynthesis.

Visible light-driven water oxidation promoted by host-guest interaction between photosensitizer and catalyst with a high quantum efficiency.

A highly active supramolecular system for visible light-driven water oxidation was developed with cyclodextrin-modified ruthenium complex as the photosensitizer, phenyl-modified ruthenium complexes as the catalysts, and sodium persulfate as the sacrificial electron acceptor. The catalysts were found to form 1:1 host-guest adducts with the photosensitizer. Stopped-flow measurement revealed the host-guest interaction is essential to facilitate the electron transfer from catalyst to sensitizer. As a result, a remarkable quantum efficiency of 84% was determined under visible light irradiation in neutral aqueous phosphate buffer. This value is nearly 1 order of magnitude higher than that of noninteraction system, indicating that the noncovalent incorporation of sensitizer and catalyst is an appealing approach for efficient conversion of solar energy into fuels.

Anchoring covalent organic polymers on supports with tunable functional groups boosting the oxygen reduction performance under pH-universal conditions.

Iron phthalocyanine (FePc) is an attractive nonprecious metal candidate for electrocatalytic oxygen reduction reaction (ORR). However, its low catalytic performance under acidic and neutral conditions limits its practical application. Herein, the FePc-based covalent organic polymers (COPFePc) polymerized in situ on the functionalized multiwalled carbon nanotubes (R-MWCNT) containing different electron-withdrawing or electron-donating groups (COPFePc/R-MWCNT, R = COOH, OH or NH2) were synthesized for ORR. Among them, COPFePc/COOH-MWCNT exhibited the best ORR performance under pH-universal conditions (acidic, neutral, and alkaline). Density-functional theory (DFT) calculations demonstrate that the electron-withdrawing or electron-donating effect of the functional groups in COPFePc/R-MWCNT causes charge redistribution of the active center Fe. The COOH functional group with an electron-withdrawing ability shifts the d-band center of Fe away from the Fermi energy level and reduces the binding strength of oxygen-containing intermediates, accelerating the ORR kinetics and optimizing the catalytic activity.

Efficient and durable oxygen reduction in alkaline media by doping heteroatomic boron into FeSA-NC catalyst.

Despite extensive research has been conducted on atomic dispersion catalysts for various reactions, altering the electronic structure of the central metal to enhance electrochemical reactivity remains a challenging task. Herein, the electrochemical reactivity was considerably enhanced by introducing heteroatomic B to adjust the d-band of single Fe center. In specific, the obtained FeSA-BNC catalyst demonstrated an outstanding ORR performance (E1/2 = 0.87 V) and exhibited greater long-term durability in alkaline media compared to Pt/C. The performance of FeSA-BNC in Zn-air battery was also higher than that of Pt/C. According to theoretical calculations, a downward shift in the d-band center of Fe was induced by introducing B, thereby improving the desorption of intermediates and facilitating the oxygen reduction reaction (ORR).

Recent Advances of the Confinement Effects Boosting Electrochemical CO2 Reduction.

Powered by clean and renewable energy, electrocatalytic CO2 reduction reaction (CO2 RR) to chemical feedstocks is an effective way to mitigate the greenhouse effect and artificially close the carbon cycle. However, the performance of electrocatalytic CO2 RR was impeded by the strong thermodynamic stability of CO2 molecules and the high susceptibility to hydrogen evolution reaction (HER) in aqueous phase systems. Moreover, the numerous reaction intermediates formed at very near potentials lead to poor selectivity of reaction products, further preventing the industrialization of CO2 RR. Catalysis in confined space can enrich the reaction intermediates to improve their coverage at the active site, increase local pH to inhibit HER, and accelerate the mass transfer rate of reactants/products and subsequently facilitate CO2 RR performance. Therefore, we summarize the research progress on the application of the confinement effects in the direction of CO2 RR in theoretical and experimental directions. We first analyzed the mechanism of the confinement effect. Subsequently, the confinement effect was discussed in various forms, which can be characterized as an abnormal catalytic phenomenon due to the relative limitation of the reaction region. In specific, based on the physical structure of the catalyst, the confinement effect was divided in four categories: pore structure confinement, cavity structure confinement, active center confinement, and other confinement methods. Based on these discussions, we also have summarized the prospects and challenges in this field. This review aims to stimulate greater interests for the development of more efficient confined strategy for CO2 RR in the future.

Enhanced electrochemical CO2 reduction performance of cobalt phthalocyanine with precise regulation of electronic states.

Herein, we report a facile strategy for constructing hybrid coordination configurations by combining functionalized graphene quantum dots (GQDs) with CoPc (CoPc/R-GQDs, with R being -NH2 or -OH) for electrochemical CO2 reduction. Benefiting from the high density of functional groups that can be provided by GQDs and the strong electron-donating property of -NH2, the examined CoPc/NH2-GQDs achieved a 100% faradaic efficiency for CO formation (FECO) at -0.8 to -0.9 V vs. RHE, and high FECO (over 90%) over a wide potential range of 500 mV. This work has presented a novel approach for catalyst design, specifically involving molecular engineering of quantum dots, which can also be applied to other essential electrochemical reactions.

Tuning the Hydroxyl Density of MXene to Regulate the Electrochemical Performance of Anchored Cobalt Phthalocyanine for CO2 Reduction.

Precise electronic state regulation through coordination environment optimization by metal-support interaction is a promising strategy to facilitate catalysis reaction, while the limited density of functional groups in the bulk substrate restricts the regulation degree. Herein, different sizes of Ti3C2Tx MXene with hydroxyl (-OH) terminal including the MXene layer (ML-OH, 3 µm), the MXene nanosheet (MNS-OH, 600 nm), and the MXene quantum dot (MQD-OH, 8 nm) were prepared to anchor CoPc, and the effect of -OH density on the performance of electrochemical CO2 reduction was systematically investigated. Notably, a linear relationship was established by plotting reactivity vs hydroxyl density. With the highest -OH density, CoPc/MQD-OH exhibits a superior Faradaic efficiency for CO formation (FECO) of ∼100% at -0.9 to -1.0 V vs RHE and a high FECO of >90% over a wide potential window from -0.8 to -1.4 V. The mechanism exploration shows that the axial coordination interaction of the -OH terminal with Co increases the electron density of the Co site, thus promoting the adsorption and activation of CO2. This work provides a new insight into designing of molecular catalysts with high efficiency and tunable structure for other electrochemical conversions.

Deep Electronic State Regulation through Unidirectional Cascade Electron Transfer Induced by Dual Junction Boosting Electrocatalysis Performance.

Unidirectional cascade electron transfer induced by multi-junctions is essential for deep electronic state regulation of the catalytic active sites, while this advanced concept has rarely been investigated in the field of electrocatalysis. In the present work, a dual junction heterostructure (FePc/L-R/CN) is designed by anchoring iron phthalocyanine (FePc)/MXene (L-Ti3 C2 -R, R═OH or F) heterojunction on g-C3 N4 nanosheet substrates for electrocatalysis. The unidirectional cascade electron transfer (g-C3 N4 → L-Ti3 C2 -R → FePc) induced by the dual junction of FePc/L-Ti3 C2 -R and L-Ti3 C2 -R/g-C3 N4 makes the Fe center electron-rich and therefore facilitates the adsorption of O2 in the oxygen reduction reaction (ORR). Moreover, the electron transfer between FePc and MXene is facilitated by the axial Fe─O coordination interaction of Fe with the OH in alkalized MXene nanosheets (L-Ti3 C2 -OH). As a result, FePc/L-OH/CN exhibits an impressive ORR activity with a half-wave potential (E1/2 ) of 0.92 V, which is superior over the catalysts with a single junction and the state-of-the-art Pt/C (E1/2 = 0.85 V). This work provides a broad idea for deep regulation of electronic state by the unidirectional cascade multi-step charge transfer and can be extended to other proton-coupled electron transfer processes.

Creating Hybrid Coordination Environment in Fe-Based Single Atom Catalyst for Efficient Oxygen Reduction.

Tailoring the local chemistry environment to optimize the geometric and electronic properties of single atom catalysts has received much attention recently. Yet, most efforts have been devoted to establishing the preferable binding between the solid support and the single metal atom. In this work, a hybrid coordination environment was created for Fe-based single atom catalysts, comprising inorganic anchoring site from the support and organic ligands from the precursor. Using N,S co-doped graphene oxide as the support, Fe phthalocyanine was selectively anchored by the N/S sites, creating the unique N/S-Fe-N4 active sites as evidenced by extended X-ray absorption fine structure and Mössbauer spectrometry. Compared with other analogues with different metal centers or support, N/S-Fe-N4 showed much improved activity in oxygen reduction reaction, delivering onset and half-wave potentials of 1.02 and 0.94 V. This was superior over the state-of-the-art 20 wt % Pt/C and the classic Fe-N4 carbon catalysts. Density functional theory calculations revealed that the interaction between phthalocyanine ligands and heteroatom dopant from the support pushed electrons of Fe site to para-position, facilitating O2 adsorption and activation. This work shows the exciting opportunities of creating a hybrid coordination environment in single atom catalysts and paves a new avenue of improving their catalytic performance.

Boosting Electrochemical Oxygen Reduction Performance of Iron Phthalocyanine through Axial Coordination Sphere Interaction.

Precise regulation of the electronic states of catalytic sites through molecular engineering is highly desired to boost catalytic performance. Herein, a facile strategy was developed to synthesize efficient oxygen reduction reaction (ORR) catalysts, based on mononuclear iron phthalocyanine supported on commercially available multi-walled carbon nanotubes that contain electron-donating functional groups (FePc/CNT-R, with "R" being -NH2 , -OH, or -COOH). These functional groups acted as axial ligands that coordinated to the Fe site, confirmed by X-ray photoelectron spectroscopy and synchrotron-radiation-based X-ray absorption fine structure. Experimental results showed that FePc/CNT-NH2 , with the most electron-donating -NH2 axial ligand, exhibited the highest ORR activity with a positive onset potential (Eonset =1.0 V vs. reversible hydrogen electrode) and half-wave potential (E1/2 =0.92 V). This was better than the state-of-the-art Pt/C catalyst (Eonset =1.00 V and E1/2 =0.85 V) under the same conditions. Overall, the functionalized FePc/CNT-R assemblies showed enhanced ORR performance in comparison to the non-functionalized FePc/CNT assembly. The origin of this behavior was investigated using density functional theory calculations, which demonstrated that the coordination of electron-donating groups to FePc facilitated the adsorption and activation of oxygen. This study not only demonstrates a series of advanced ORR electrocatalysts, but also introduces a feasible strategy for the rational design of highly active electrocatalysts for other proton-coupled electron transfer reactions.

Novel piperidinium-based ionic liquid as electrolyte additive for high voltage lithium-ion batteries.

Conventional carbonate-based electrolyte is prone to oxidative decomposition at high voltage (over 4.5 V vs. Li/Li+), which leads to the bad oxidation stability and inferior cycling performance of lithium ion batteries (LIBs). To solve these problems, a novel ionic liquid (IL) N-butyronitrile-N-methylpiperidinium bis(fluorosulfonyl)imide (PP1,CNFSI) was synthesized and explored as the additive to the LiPF6-ethylene carbonate (EC)/dimethyl carbonate (DMC) electrolyte. For the cell performance, the addition of PP1,CNFSI not only inhibits overcharge phenomenon, but also improves discharge capacity, thus enhancing capacity retention capability. Compared to the cell with blank electrolyte, the capacity retentions of adding 15 wt% PP1,CNFSI into the electrolyte were improved to 96.8% and 97% from 82.8% and 78.7% at 0.2 C and 5 C, respectively. The effects of PP1,CNFSI on the LNMO cathode surface were further investigated by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). It reveals that PP1,CNFSI addition drives the formation of solid electrolyte interphase (SEI) film which suppresses oxidative decomposition of the electrolyte and protects the structure cathode material.

Homogeneous Catalysts Based on First-Row Transition-Metals for Electrochemical Water Oxidation.

Strategies that enable the renewable production of storable fuels (i. e. hydrogen or hydrocarbons) through electrocatalysis continue to generate interest in the scientific community. Of central importance to this pursuit is obtaining the requisite chemical (H+ ) and electronic (e- ) inputs for fuel-forming reduction reactions, which can be met sustainably by water oxidation catalysis. Further possibility exists to couple these redox transformations to renewable energy sources (i. e. solar), thus creating a carbon neutral solution for long-term energy storage. Nature uses a Mn-Ca cluster for water oxidation catalysis via multiple proton-coupled electron-transfers (PCETs) with a photogenerated bias to perform this process with TOF 100∼300 s-1 . Synthetic molecular catalysts that efficiently perform this conversion commonly utilize rare metals (e. g., Ru, Ir), whose low abundance are associated to higher costs and scalability limitations. Inspired by nature's use of 1st row transition metal (TM) complexes for water oxidation catalysts (WOCs), attempts to use these abundant metals have been intensively explored but met with limited success. The smaller atomic size of 1st row TM ions lowers its ability to accommodate the oxidative equivalents required in the 4e- /4H+ water oxidation catalysis process, unlike noble metal catalysts that perform single-site electrocatalysis at lower overpotentials (η). Overcoming the limitations of 1st row TMs requires developing molecular catalysts that exploit biomimetic phenomena - multiple-metal redox-cooperativity, PCET and second-sphere interactions - to lower the overpotential, preorganize substrates and maintain stability. Thus, the ultimate goal of developing efficient, robust and scalable WOCs remains a challenge. This Review provides a summary of previous research works highlighting 1st row TM-based homogeneous WOCs, catalytic mechanisms, followed by strategies for catalytic activity improvements, before closing with a future outlook for this field.

Control over Electrochemical CO2 Reduction Selectivity by Coordination Engineering of Tin Single-Atom Catalysts.

Carbon-based single-atom catalysts (SACs) with well-defined and homogeneously dispersed metal-N4 moieties provide a great opportunity for CO2 reduction. However, controlling the binding strength of various reactive intermediates on catalyst surface is necessary to enhance the selectivity to a desired product, and it is still a challenge. In this work, the authors prepared Sn SACs consisting of atomically dispersed SnN3 O1 active sites supported on N-rich carbon matrix (Sn-NOC) for efficient electrochemical CO2 reduction. Contrary to the classic Sn-N4 configuration which gives HCOOH and H2 as the predominant products, Sn-NOC with asymmetric atomic interface of SnN3 O1 gives CO as the exclusive product. Experimental results and density functional theory calculations show that the atomic arrangement of SnN3 O1 reduces the activation energy for *COO and *COOH formation, while increasing energy barrier for HCOO* formation significantly, thereby facilitating CO2 -to-CO conversion and suppressing HCOOH production. This work provides a new way for enhancing the selectivity to a specific product by controlling individually the binding strength of each reactive intermediate on catalyst surface.

Potential- and Buffer-Dependent Catalyst Decomposition during Nickel-Based Water Oxidation Catalysis.

The production of hydrogen by water electrolysis benefits from the development of water oxidation catalysts. This development process can be aided by the postulation of design rules for catalytic systems. The analysis of the reactivity of molecular complexes can be complicated by their decomposition under catalytic conditions into nanoparticles that may also be active. Such a misinterpretation can lead to incorrect design rules. In this study, the nickel-based water oxidation catalyst [NiII (meso-L)](ClO4 )2 , which was previously thought to operate as a molecular catalyst, is found to decompose to form a NiOx layer in a pH 7.0 phosphate buffer under prolonged catalytic conditions, as indicated by controlled potential electrolysis, electrochemical quartz crystal microbalance, and X-ray photoelectron spectroscopy measurements. Interestingly, the formed NiOx layer desorbs from the surface of the electrode under less anodic potentials. Therefore, no nickel species can be detected on the electrode after electrolysis. Catalyst decomposition is strongly dependent on the pH and buffer, as there is no indication of NiOx layer formation at pH 6.5 in phosphate buffer nor in a pH 7.0 acetate buffer. Under these conditions, the activity stems from a molecular species, but currents are much lower. This study demonstrates the importance of in situ characterization methods for catalyst decomposition and metal oxide layer formation, and previously proposed design elements for nickel-based catalysts need to be revised.

Nickel is a Different Pickle: Trends in Water Oxidation Catalysis for Molecular Nickel Complexes.

The development of novel water oxidation catalysts is important in the context of renewable fuels production. Ligand design is one of the key tools to improve the activity and stability of molecular catalysts. The establishment of ligand design rules can facilitate the development of improved molecular catalysts. In this paper it is shown that chemical oxidants can be used to probe oxygen evolution activity for nickel-based systems, and trends are reported that can improve future ligand design. Interestingly, different ligand effects were observed in comparison to other first-row transition metal complexes. For example, nickel complexes with secondary amine donors were more active than with tertiary amine donors, which is the opposite for iron complexes. The incorporation of imine donor groups in a cyclam ligand resulted in the fastest and most durable nickel catalyst of our series, achieving oxygen evolution turnover numbers up to 380 and turnover frequencies up to 68 min-1 in a pH 5.0 acetate buffer using Oxone as oxidant. Initial kinetic experiments with this catalyst revealed a first order in chemical oxidant and a half order in catalyst. This implies a rate-determining oxidation step from a dimeric species that needs to break up to generate the active catalyst. These findings lay the foundation for the rational design of molecular nickel catalysts for water oxidation and highlight that catalyst design rules are not generally applicable for different metals.