Active Center Research Articles

Bimetallic Sulfur-Doped Nickel-Cobalt Selenides as Efficient Bifunctional Electrocatalysts for the Complete Decomposition of Water.

The creation and enhancement of non-precious metal bifunctional catalysts with superior stability and stabilizing activity is necessary to achieve water splitting in alkaline media. The paper presents a method for preparing nickel-cobalt bimetallic selenides (NiCo-Sex/CF) using a combination of hydrothermal and high-temperature selenization techniques. NiCo-Sex/CF shows great potential as a catalyst for water separation. The catalyst's electronic structure and active centre can be modified by double doping with sulfur and selenium, resulting in increased selectivity and activity under varying reaction conditions. This method also offers the benefits of a simple preparation process and applicability to a wide range of catalytic reactions. Experimental results demonstrate that an overpotential of 194 mV produces a current density of 10 mA cm-2 when using this electrocatalyst as an OER catalyst. When used as a HER catalyst, the electrocatalyst required an overpotential of only 76 mV to generate a current density of 10 mA cm-2.Furthermore, a voltage of 1.5 V can drive the overall decomposition of water to achieve a current density of 10 mA cm-2. This study highlights the potential of sulfur-selenide double-doped catalysts for both scientific research and practical applications.

Higher phosphorus and water use efficiencies and leaf stoichiometry contribute to legume success in drylands

Abstract Legumes are essential plants in dryland ecosystems worldwide because they increase nitrogen availability, so their understanding is vital for improving knowledge and modelling in the face of climate change. This work studies the differences in resource use efficiency and their relationship with photosynthetic, photochemical, bioelemental, and stoichiometric traits of coexistent legumes and non‐legumes in a Sonoran Desert ecosystem. We found that legumes had higher photosynthetic rates, intrinsic and seasonal water use efficiency (WUE), phosphorus use efficiency (PPUE), and higher light utilisation mediated by chlorophyll content and active reaction centers, which may increase their photoprotection. Legumes can increase their WUE and PPUE with no changes in nitrogen use efficiency (PNUE). Consequently, observed trait relationships between studied traits in these legumes have significant differences with the non‐legume species in the study. Stoichiometry is helpful, in some cases, as an indicator of nutrient use efficiency and enables functional group differentiation. Our results strongly relate legumes' higher resource use efficiency with their success in dryland ecosystems. Read the free Plain Language Summary for this article on the Journal blog.

Structure of the carboxypeptidase t from <i>Thermoactinomyces vulgaris</i> complex with <i>L</i> - phenyl lactate

The crystal structure of the metallocarboxypeptidase T from Thermoactinomyces vulgaris complex with L-phenylactate was obtained with a resolution of 1.73 Å. Unlike pancreatic carboxypeptidase A, which binds one L-phenylactate molecule, in complex with CPT, the ligand occupies both S1 and S1ʹ sites of the active center simultaneously. In this case, conformational changes occur that differ from the changes caused by the alternate occupation of the S1 and S1ʹ sites by BOC-leucine and benzylsuccinic acid. These changes concern the residues E277, E59, L254, G192, S127 and Y218 and reach a span of 0.77 Å. A conclusion is made about the possible role of these residues in the recognition and catalysis of substrates by carboxypeptidase T.

Electrochemically Created Active Centers in a Bimetallic CoNi-Triazole Metal-Organic Framework for Enhanced Oxygen Evolution Reaction Activity.

Electrochemical water oxidation utilizing bimetallic CoNi-Tz (Tz = 1,2,4-triazole) framework is explored. Initially, CoNi-Tz possesses active tetrahedral Co center and electron-mediated octahedral Ni chain. After performing an electrochemical activation, the partial structural transformation on the Ni center occurs. This leads to the generation of excessive active centers which can promote catalytic activity of the framework. The activated CoNi-Tz catalyst displays a remarkably low OER overpotential of 293 mV at a current density of 10 mA cm-2 with a small Tafel slope of 49.98 mV dec-1, outperforming the single metal Co-Tz and benchmark IrO2 catalysts.

Enhanced Performance for Li & Na Ion Battery Anodes by Charge Modulation of Interface Through SiC4 and SiN1C3 Active Centers on Silicon Nitrogen Co‐Doped Graphene

AbstractHeteroatom doping of graphene is a powerful approach to develop high‐performance Li and Na ion battery anodes. In this study, silicon‐nitrogen co‐doped graphene (Si−N−GN) nanostructures were successfully synthesized via a rational and scalable solvothermal process. The performances of Si−N−GN in Na+ and Li+ half‐cells were investigated in detail by advanced electrochemical techniques and the obtained results were analyzed in terms of Si−N−GN surface properties, reaction kinetics, and electrode/interface interactions. Si−N−GN exhibited a superior capacity of 540 mAh g−1 at a current density of 0.5 A g−1 for Li+ and improved rate capability for both Li+ and Na+ which are linked with the increased interlayer spacing and enlarged graphene sheets upon Si‐doping. Importantly, the capacity increased with the number of cycles owing to surface electron density redistribution and Si−N−GN/SEI interactions, supported by DFT.

Biomimetic Electronic Communication of Iodine Doped Single-Atom Fe Site for Highly Active and Stable Dopamine Oxidation.

Rational design of highly active and stable catalysts for dopamine oxidation is still a great challenge. Herein, inspired by the catalytic pocket of natural enzymes, an iodine (I)-doped single Fe-site catalyst (I/FeSANC) is synthesized to mimic the catalytic center of heme enzymes in both geometrical and electronic structures, aiming to enhance dopamine (DA) oxidation. Experimental studies and theoretical calculations show that electronic communication between I and FeN5 effectively modulates the electronic structure of the active site, greatly optimizing the overlap of Fe 3d and O 2p orbitals, thereby enhancing OH adsorption. In addition, the electronic communication induced by iodine doping attenuates the attack of proton hydrogen on the active center, thereby enhancing the stability of I/FeSANC. This work provides new insights into the design of highly active and stable single-atom catalysts and enhances the understanding of catalytic mechanisms for DA oxidation at the atomic scale.

A Novel Composite Material UiO-66-Br@MBC for Mercury Removal from Flue Gas: Preparation and Mechanism.

To reduce the mercury content in flue gas from coal-fired power plants and to obtain high-performance, low-cost mercury adsorbents, a novel composite material was prepared by structural design through the in situ growth method. Functionalization treatments such as the modification of functional groups and multilayer loading of polymetallic were conducted. These materials include the MOF material UiO-66 and modified biochar doped with Fe/Ce polymetallic, both of which contain unsaturated metal centrals and oxygen-containing functional groups. On the basis of obtaining the effects of adsorption temperature and composite ratio on the Hg0 removal characteristics, coupling and synergistic mechanisms between the various types of active centers included were investigated by using a variety of characterization and analysis tools. The active adsorption sites and oxidation sites were identified during this process, and the constitutive relationship between the physicochemical properties and the performance of Hg0 removal was established. The temperature-programmed desorption technique, Grand Canonical Monte Carlo simulation, and adsorption kinetic model were employed to reveal the mechanism of Hg0 removal. The results showed that the UiO-66-Br@MBC composite adsorbent possessed an excellent Hg0 removal performance at adsorption temperatures ranging from 50 to 250 °C, and targeted construction of adsorption and oxidation sites while maintaining thermal stability. The Hg0 removal by the composites is the result of both adsorption and oxidation. The micropores and small pore mesopores in the samples provide physical adsorption sites. The modified biochar acts as a carrier to facilitate the full exposure of the central metal zirconium ions, the formation of more active sites, and the process of electron transfer. The doping modification of the Br element can enhance the overall redox ability of the sample, and the introduced Fe and Ce polymetallic ions can work in concert to promote the oxidation process of Hg0. The excellent regulation of the ratio between adsorption and oxidation sites on the surface of the composite material finally led to a significant boost in the samples' capacity to remove Hg0.

Atomically Engineered Chlorine Coordination of Iron in Active Centers for Selectively Catalytic H2O2 Decomposition Toward Efficient Antitumor-Specific Therapy.

The intervention of endogenous H2O2 via nanozymes provides a potential antitumor-specific therapy; however, the role of the nanozyme structure in relation to the selective decomposition of H2O2 to hydroxyl radicals (•OH) is yet to be fully understood, which limits the development of this therapeutic approaches. Herein, an iron single-atom nanozyme (Fe─N2Cl2─C SAzyme) is reported, which is prepared through precise Fe─Cl coordination based on the construction of a characteristic Fe-containing molecule. Fe─N2Cl2─C exhibits efficient catalytic H2O2 decomposition (2.19 × 106 mm-1 s-1), which is the highest among reported SAzymes. More importantly, it is found that H2O2 selectively decomposed into •OH on the Fe─N2Cl2─C surface, which is attributable to the d orbitals of the Fe active center matching the O-2p electrons of the adsorbed hydroxide (*OH) intermediate. Fe─N2Cl2─C is strongly cytotoxic toward a variety of cancer-cell lines in vitro but not to normal cells. Furthermore, Fe─N2Cl2─C shows an outstanding specific therapeutic effect in vivo; it efficiently destroys solid malignant tumors without injuring normal tissue. Altogether, these findings highlight the selective catalytic decomposition of H2O2 to •OH, which is achieved by engineering the active center on the atomic level, thereby providing an avenue for the development of specific nanomedicines with efficient antitumor activities.

Role of selenium in the pathophysiology of cardiorenal anaemia syndrome.

Chronic kidney disease (CKD) and cardiovascular disease (CVD) have multiple bidirectional mechanisms, and anaemia is one of the critical factors that are associated with the progression of the two disorders [referred to as cardiorenal anaemia syndrome (CRAS)]. Several lines of evidence indicate that CRAS confers a worse prognosis, suggesting the need to clarify the underlying pathophysiology. Among the micronutrients (trace elements) that are essential to humans, inadequate iron status has previously been implicated in the pathogenesis of CRAS; however, the roles of other trace elements remain unclear. Selenium critically regulates the function of selenoproteins, in which selenocysteine is present at the active centres. The human genome encodes 25 selenoproteins, and accumulating data indicate that they regulate diverse physiological processes, including cellular redox homeostasis, calcium flux, thyroid hormone activity and haematopoiesis, all of which directly or indirectly influence cardiac function. The essential role of selenium in human health is underscored by the fact that its deficiency results in multiple disorders, among which are cardiomyopathy and abnormal erythrocyte morphology. Studies have shown that selenium deficiency is not uncommon in CKD patients with poor nutritional status, suggesting that it may be an under-recognized cause of anaemia and cardiovascular disorders in these patients. In this review, we discuss the role of selenium in the pathophysiology of CKD, particularly in the context of the interconnection among CKD, cardiac dysfunction and anaemia. Given that selenium deficiency is associated with treatment-resistant anaemia and an increased risk of CVD, its role as a key modulator of CRAS merits future investigation.

Identification and molecular mechanism of novel antioxidant peptide from fish sauce: A combined quantum chemistry and molecular simulation

Fish sauce, derived from fermented fish, exhibits a notable antioxidant effect after a six-month fermentation process, and we propose that potential antioxidant peptides were present in the fish sauce. We isolated, purified, and identified potential bioactive antioxidant peptides by using fish sauce fermented for 6 months. Additionally, molecular simulation was employed to investigate the antioxidant action mechanism of these bioactive peptides. The molecular docking results revealed that FS4-1 (MHQLSKK), FS4-2 (VLDNSPER), FS4-3 (MNPPAASIK), FS6-1(VLKQAAAGR), and FS6-2 (SPDVSPRR), could dock with the Keap1 receptor. The primary force (Van der Waals' force and hydrogen bonds) and key sites (GLY509 and ALA510) of Keap1 binding to peptides were determined. The active center was located in the side chain of amino acid Met at positions C7H78 and C7H79. We here identified antioxidant peptides in fish sauce and revealed the antioxidant mechanism through molecular simulations.

Modifying the Charge-Density of Tetrahedral Cobalt(II) Centers through Carbon-Layer Modulation Promotes C-H Activation in the Propane Dehydrogenation Reaction (PDH).

The electronic structure of active metal centers plays an indispensable role in regulating catalytic reactivity in heterogeneous catalysis, developing other metals as promoters to decorate electronic state is a common strategy, while non-metal component of carbon as electronic additives to regulate d-band center has rarely been studied in thermal-catalysis field. Herein, we report electron-deficient tetrahedral Co(II) (Td-cobalt(II)) centers through carbon-layer modulation for propane dehydrogenation (PDH). It is indicated that bifunctional sites of both Td-cobalt(II) and metallic-cobalt are designed, and the in situ generated carbon through the disproportionation of CO on metallic-cobalt can cover the inactive metallic-cobalt and tailor d-band of active Td-cobalt(II) simultaneously. More importantly, the pre-deposited carbon-layer is proposed to decrease electron density of Td-cobalt(II) and make d-band center closer to Fermi level, consequently promotes C-H activation in PDH reaction. This study provides new perspective for the utilization of inactive carbon as electronic promoters and unlocks new opportunity to fabricate efficient PDH and other heterogeneous catalysts.

Synergistic Coordination in Cu Single-Atom Catalysts Enhances High-Valent Copper-Oxo Species for Efficient PMS Activation.

In the domain of heterogeneous catalytic activation of peroxymonosulfate (PMS), high-valent metal-oxo (HVMO) species are widely recognized as potent oxidants for the abatement of organic pollutants. However, the generation selectivity and efficiency of HVMO are often constrained by stringent requirements for catalyst adsorption sites and electron transfer efficiency. In this study, a single-atom catalyst, CuSA/CNP&S, is synthesized featuring multiple types (planar/axial) of heteroatom coordination via an H-bond-assisted self-assembly strategy. It isconfirmed that CuN3 active centers with axial S coordination are uniformly distributed in a carbon matrix modified by planar P atoms. CuSA/CNP&S activated PMS to selectively generate Cu(III)═OH species as the primary reactive oxygen species (ROS). The pseudo-first-order kinetic rate for bisphenol A degradation reached 1.51min-1, a 17.57-fold increase compared to the unmodified CuSA/CN catalyst. Additionally, the CuSA/CNP&S catalyst demonstrates high efficiency and durability in removing contaminants from various aqueous matrices. Theoretical calculations and experimental results indicate that the intrinsic electric field generated by distal planar P atoms enhances electron transfer efficiency within the carbon matrix. Meanwhile, axial S coordination elevates the d-band center and tunes the eg * band broadening of Cu, thereby enhancing the adsorption selectivity for the terminal oxygen of PMS. This multitype coordination synergistically mitigates the issues of low selectivity and yield of HVMO species.

Cerium-doped construction of oxygen vacancies in IrO2 to promote acidic OER reaction

Proton exchange membrane electrolysis of water is currently recognized in the world as an up-and-coming method for the preparation of green hydrogen energy. Due to its sustainability and low pollution, it has attracted much attention from practitioners recently. The most advanced iridium oxide (IrO2) is the most promising catalyst.However, developing a highly efficient and stable IrO2 catalyst that can adapt to industrial conditions remains a terrific challenge. One of the main problems to be solved is that the slow oxygen evolution reaction(OER) at the anode limits the production of hydrogen. We propose a straightforward method for synthesizing Ce metal-doped IrO2 with a high oxygen vacancy concentration while simultaneously improving the IrO2 catalytic activity and stability.The Ce-doped IrO2 (Ce-IrO2) exhibits a microscopic nanoparticle morphology and a high density of oxygen vacancies, enabling a rapid oxygen evolution reaction (OER) process with a low overpotential of 240 mV at 10 mA·cm-2 and a remarkable stability of over 50 h under acidic conditions.A growing body of research shows a synergistic effect of oxygen vacancies and mental dopants on the adsorption and evolution of active intermediates in the active center so that the oxygen evolution reaction activity of the Ir-based catalyst can be improved. We hope that ourwork will provide a sample method for acquiring catalysts capable of adapting to a wide range of conditions via metal doping.

Sulfur Modified Carbon-Based Single-Atom Catalysts for Electrocatalytic Reactions.

Efficient and sustainable energy development is a powerful tool for addressing the energy and environmental crises. Single-atom catalysts (SACs) have received high attention for their extremely high atom utilization efficiency and excellent catalytic activity, and have broad application prospects in energy development and chemical production. M-N4 is an active center model with clear catalytic activity, but its catalytic properties such as catalytic activity, selectivity, and durability need to be further improved. Adjustment of the coordination environment of the central metal by incorporating heteroatoms (e.g., sulfur) is an effective and feasible modification method. This paper describes the precise synthetic methods for introducing sulfur atoms into M-N4 and controlling whether they are directly coordinated with the central metal to form a specific coordination configuration, the application of sulfur-doped carbon-based single-atom catalysts in electrocatalytic reactions such as ORR, CO2RR, HER, OER, and other electrocatalytic reaction are systematically reviewed. Meanwhile, the effect of the tuning of the electronic structure and ligand configuration parameters of the active center due to doped sulfur atoms with the improvement of catalytic performance is introduced by combining different characterization and testing methods. Finally, several opinions on development of sulfur-doped carbon-based SACs are put forward.

Breaking the stability limit of zeolite-based alkane dehydrogenation catalysts

Metal catalysts confined inside zeolite micropores or crystals are widely applied in the chemical industry because of their distinctive catalytic functions, especially with regard to the conversion of small and stable alkane molecules [1,2]. Silicalite-1 (S-1), a pure silica zeolite with an MFI topology, has a robust framework capable of withstanding harsh thermal and chemical conditions. Recently, S-1-based catalysts have demonstrated significant advantages in the construction and stabilization of various active metal centers and have attracted considerable attention for their potential in alkane dehydrogenation reactions. The absence of acidic sites prevents various acid-catalyzed side reactions, rendering S-1 a promising candidate for high-temperature reactions such as non-oxidative propane dehydrogenation (PDH). Sun et al. revealed that encapsulating subnanometer bimetallic PtZn clusters in S-1 resulted in a high propylene selectivity of 99%, with no catalyst deactivation even after 200h in the PDH reaction [3]. However, sustaining high stability at high conversion rates is still challenging for PDH reactions, and commercial processes are still based on Pt- and Cr-based catalysts, which need frequent regeneration.

Formation of active centers of polymer catalysts for radical-coordination polymerization

Chromatography–mass spectrometry of samples representing the interaction products of ferrocene, radical initiator and monomer taken in the molar ratio of 1:2:10 in toluene solution was used for experimental detection of products indicating the structure and mechanism of formation of metal complex active centers of radical-coordination polymerization. Structures similar to those proposed by the quantum-chemical modeling were demonstrated to be formed with the participation of secondary radicals.

Developments of Pyrrolo[2,3-d]pyrimidines with Pharmaceutical Potential

: In terms of fused heterocyclic compounds, pyrrolopyrimidines, and their substituted analogs are among the most extensively explored scaffolds. Based on the location of the nitrogen atom in the pyrrole ring, pyrrolopyrimidines have different isomers. This study deals only with the pyrrolo[2,3-d]pyrimidine isomer. Several techniques are represented and discussed in this review for producing pyrrolo[2,3-d]pyrimidine derivatives. The first one is the cyclization of the pyrimidine ring on the pyrrole ring through the reaction of β-enaminonitrile, β-enaminoester or β-enaminoamide of the pyrrole ring with different bifunctional reagents such as formic acid, acetic acid, acetic anhydride, formamide, isothiocyanate, urea, thiourea, and carbon disulfide. The second technique includes cyclization of the pyrrole ring on the pyrimidine ring via the treatment of pyrimidine, aminopyrimidine, diamino-pyrimidine, or triamino-pyrimidine with different reagents such as nitroalkenes, alkynes, aldehydes, and acid chlorides. In addition, different reaction methodologies like one pot, two-step, and threestep synthetic methodologies were reported. The last technique for producing pyrrolo[2,3-d]pyrimidine derivatives is through miscellaneous reactions. This review also includes the interactions of pyrrolo[2,3- d]pyrimidines at different active centers of the pyrrole ring with different reagents to form N-alkylated, Nglycosylated, C-5, and C-6 adducts. Besides, the interactions on the pyrimidine ring to form chloro, hydrazino, and amino-imino derivatives were also discussed. The amino-imino derivatives are key intermediates for the preparation of tricyclic pyrrolotriazolopyrimidines. Finally, the pharmaceutical and biological properties of some pyrrolo[2,3-d]pyrimidine derivatives have also been mentioned. This information can be utilized to design novel diverse pyrrolopyrimidine derivatives for recent challenges in pharmaceutical and medical studies to develop the already existing drugs or discover new ones.

BiW11/Porous carbon nitride catalyst improves charge carrier separation efficiency for enhanced photocatalytic hydrogen evolution

Solar water splitting has received tremendous attention as hydrogen emerges as a promising energy carrier. Carbon nitride (CN) is an ideal candidate for H2 evolution via water splitting on account of its unique optical and electrical properties. To mitigate photoexcited charge carriers recombination that has severely limited the photocatalytic activity of CN, a heterojunction photocatalyst of CN with monovacant bismuth tungstate (Na6[BiW11O38H]·22H2O, noted as BiW11) as a highly efficient photocatalyst is designed. Herein, the porous carbon nitride (PCN) is first fabricated via the gas template method, and then PCN with BiW11 is modified via the impregnation method. Series of BiW11-based PCN composites with different BiW11 loadings (BiW11/PCN-x, x represents the amount of BiW11) are created to merge complementary advantages of both materials. Visible-light-driven photocatalytic properties of BiW11/PCN-x composites have been examined with Na2S/Na2SO3 sacrificial agents. The hydrogen evolution rate of the BiW11/PCN-10 is 2.45 and 1.98 times than that of PCN and BiW11. This extraordinary photocatalytic activity is ascribed to increased attachment sites for catalysts and active centers for hydrogen reduction due to porous structure and significantly facilitated charge separation efficiency through the type-II heterostructure. The resulting composites would be a potential candidate strategy for the design of highly efficient polyoxomatalate-based photocatalysts for efficient hydrogen production applications.

Rapeseed cake meal extract as an eco-friendly green sustainable inhibitor for the corrosion of cold rolled steel in trichloroacetic acid solution

The inhibitory properties of rapeseed cake meal extract (RCME) on the corrosion of cold rolled steel (CRS) in trichloroacetic acid (TCA) were systematically investigated using gravimetric, electrochemical, surface characterizations and theoretical calculations. The results demonstrate that RCME exhibits excellent inhibitory performance with a maximum inhibition efficiency of 92.7% for 100 mg L−1 RCME at 20°C. The adsorption of RCME obeys Langmuir isotherm at 20 and 30°C, Temkin isotherm at 40°C, and Freundlich isotherm at 50°C. RCME acts as a cathodic inhibitor. The charge transfer resistance is increased with the addition of RCME, while the double-layer capacitance decreases. SEM, AFM, CLSM, XPS, XRD and TOF-SIMS analyses confirm that the active components in RCME adsorb onto the surface of CRS, forming a protective film that effectively inhibits the corrosion of CRS by TCA. Along with the increase in the concentration of RCME, the surface tension of the inhibited solution gradually decreases, while the electrical conductivity increases before stabilizing. HPLC-MS and FTIR analyses reveal rutin, linolenic acid, linoleic acid and adenine are the effective substances in RCME. Quantum chemical (QC) calculations and molecular dynamic (MD) simulations indicate that the active centers of the effective inhibitor molecules are predominantly located on benzene rings, O- or N-containing heterocyclic rings, and functional groups such as C=O and C=C. Additionally, their main chains adsorb onto the Fe (001) surface in an approximately flat manner, involving both chemical and physical adsorption processes.

Nickel single-atom synergistic iron-nitrogen sites for efficient CO2 electroreduction at a wide potential range

Recently, diatomic site catalysts (DASCs) by introducing a second metal active site have become a research focus in electrochemical CO2 reduction reaction (eCO2RR), as can regulate electronic structure of metal centers and optimize reaction free energies. However, hitherto the studies on the origin of the outstanding performance of DASCs and the accurate identification of active centers are not still clear. Herein, we designed a nickel–iron diatomic site catalyst by loading highly dispersed iron phthalocyanine (FePc) on a nickel single-atom with ultrathin porous nitrogen-doped carbon nanosheet substrate (denoted as FePc/M-LNi-NC). Experimental and calculational results prove that the synergistic catalysis of FePc and carbon nanosheet based Ni single-atom endowed FePc/M-LNi-NC achieving excellent CO2 reduction performance with a maximum CO Faradaic efficiency of 98.8 % at –0.8 V vs. RHE. In particular, the current density of FePc/M-LNi-NC at −1.0 V vs. RHE in an H-type cell (−20.9 mA/cm2) is 5.6 times that of FePc (3.7 mA/cm2). Compared with M-LNi-NC, the potential range of FePc/M-LNi-NC when FECO above 95 % expands from 0.31 to 0.43 V. Density functional theory calculations reveal that the Fe site in FePc/M-LNi-NC has a lower free energy change for *COOH formation (ΔG*COOH) and CO desorption (ΔGCO) than Ni site, thus exhibits higher electrocatalytic activity. Furthermore, the ΔG*COOH on FePc/M-LNi-NC declines from 0.78 to 0.08 eV compared to M-LNi-NC, and the ΔGCO lowers from 1.36 to 0.33 eV compared to FePc, thus FePc/M-LNi-NC achieves high performance for eCO2RR at a wide potential range.