Dispersed Metal Catalysts Research Articles

Uniformly Dispersed Cobalt Catalyst on the Coffee Waste-Derived Carbon Support for Hydrogen Evolution Reaction

The research interests in transition metal catalysts on carbon support have increased last decade for expensive noble metal catalyst replacement. Because those catalysts have a large surface area, good chemical stability, and are cheap and earth-abundant. Mainly structured with Co-N-C catalysts such as Cobalt (Co) nanoparticle embedded N-doped carbon, Co single-atom catalyst on carbon, etc., are highly efficient for hydrogen evolution reaction (HER) in acidic and alkaline electrolytes.Here, we report the uniformly dispersed cobalt catalysts (Co-SCC-N) on nitrogen (N)-doped spent coffee grounds (SCG) derived carbon support, which was further utilized as HER electrocatalyst. In the first step, SCG-derived carbon is synthesized by simple pyrolysis with ZnCl2. Then, the cobalt catalyst is prepared by adsorption of the complex Co ion with 1,10-phenanthroline on the SCG-derived carbon support, followed by pyrolysis at 800°C under a nitrogen atmosphere. Uniform and high dispersions of cobalt on the carbon substrate have been confirmed by scanning transmission electron microscopy (STEM) and energy dispersive X-ray (EDX) elemental mapping analysis. X-ray photoelectron spectroscopy (XPS) determined that the catalyst contained Co2+ ions and had nitrogen-doped. Also, X-ray diffraction (XRD) and Raman spectroscopy revealed carbon materials disorders, crystallinity, and no metal-related peaks that validated no metal clusters on the carbon. Electrochemical tests were examined by linear sweep voltammetry, Tafel, electrochemical impedance spectroscopy, and chronopotentiometry (CP) in alkaline and acidic electrolytes. Co-SCC-N exhibited excellent HER performance in an alkaline medium, which needed 0.246 V to reach 10 mA cm-2. And the CP test confirmed better stability at 10 mA cm-2 for 12 hours. The result recommends a simple synthesis method for uniformly dispersed metal catalysts on biomass-derived carbon support by a simple pyrolysis technique.

Chemical Kinetics of Metal Single Atom and Nanocluster Formation on Surfaces: An Example of Pt on Hexagonal Boron Nitride.

The production of atomically dispersed metal catalysts remains a significant challenge in the field of heterogeneous catalysis due to coexistence with continuously packed sites such as nanoclusters and nanoparticles. This work presents a comprehensive guidance on how to increase the degree of atomization through a selection of appropriate experimental conditions and supports. It is based on a rigorous macro-kinetic theory that captures relevant competing processes of nucleation and formation of single atoms stabilized by point defects. The effects of metal-support interactions and deposition parameters on the resulting single atom to nanocluster ratio as well as the role of metal centers formed on point defects in the kinetics of nucleation have been established, thus paving the way to guided synthesis of single atom catalysts. The predictions are supported by experimental results on sputter deposition of Pt on exfoliated hexagonal boron nitride, as imaged by aberration-corrected scanning transmission electron microscopy.

Lignite-char-supported highly dispersed ultrasmall Ni-Co alloy for stably dry reforming of methane at low temperature

Lignite, abundant in oxygen-containing functional groups, can disperse metal ions through an ion-exchanging method to prepare highly dispersed metal catalysts. Herein, we prepared the Ni-Co bimetallic catalysts using this method and tested their activity and stability in the dry reforming of methane reaction. The Ni0.05-Co0.1 with Ni/Co mass ratio of 1:10 exhibited superior performance due to its higher specific surface area (386 m2/g), smaller metallic particle size (4.85 nm), better dispersion and moderate basicity (0.023 mmol/g), showing the best activity at 650 °C, 2400 mL.h−1.g−1 and atmospheric pressure, with a conversion of 71.5% for CH4, 82.8% for CO2, and a molar ratio of H2/CO of 0.73. Additionally, the catalyst maintained a stable activity throughout a continuous 30 h test at 650 °C, 7200 mL.h−1.g−1 and 0.3 MPa. Overall, this study demonstrates that lignite-char-supported Ni-Co alloy catalysts show great potential for DRM reaction particularly at relatively low temperature and elevated pressure.

Binary NiCo nanoalloys and single-atoms implanted nitrogen-doped carbon nanotubes as highly efficient, robust electrocatalyst for overall water splitting

Finding robust, high-efficiency, noble-metal-free electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) particularly at a low overpotential is a crucial endeavor for water electrolyzer-based green H2 harvesting, but challenges remain. Fortunately, atomically dispersed metal catalysts hold great potential for OER and HER owing to the exclusive electronic structure and maximized atom utilization, however, the insufficient population of reactive sites and unfortunate electrical conductivity seriously limit their performance. Herein, we rationally designed and synthesized a single-atom catalyst consisting of atomic Co and Ni with NiCo alloys encapsulated nitrogen-doped carbon nanotubes (N-CNTs). The NiCo-N-CNTs catalyst annealed at 900 °C (NiCo-N-CNTs-900) displays ultralow overpotential of 210 mV and 54 mV at 10 mA/cm2 for OER and HER, respectively, which are attributed to the robust synergistic effects of Ni/Co single atoms and NiCo nanoalloys. Furthermore, NiCo-N-CNTs-900 electrode exhibits higher mass activity of 2188 A/gNiCo and 468.75 A/gNiCo and turnover frequency of 0.679 O2 s−1 and 0.285 H2 s−1 for OER and HER, respectively, which is much better than those of commercial RuO2 and Pt/C catalysts. We further employed the NiCo-N-CNTs-900 as both anode and cathode catalyst for constructing a two-electrode electrolyzer, generating a current density of 10 mA/cm2 at a low cell voltage of 1.483 V, surpassing the benchmark Pt/C//RuO2 pair. This work not only provides a robust and effective non-precious metal catalyst but also a facile, efficient method to fabricate atomically dispersed metal atoms integrated with alloys for clean hydrogen production and beyond.

Transition Metal (Fe, Zn, Co, and Ni) Single-Atom Catalysts Anchored on N,S-Codoped Hybrid Nanocarbons for Oxygen Reduction Reaction

Atomically dispersed transition metal catalysts have served as promising candidates to substitute noble metals in energy conversion. A majority of carbon-supported transition metal single-atom catalysts (SACs) have been synthesized via the high-temperature sintering method, in which the complex heating and cooling processes are time- and energy-consuming. Herein, we have developed a simple and highly effective microwave-assisted heating method to prepare a series of isolated transition metal SACs anchored on a N,S-codoped nanocarbon matrix, which are denoted as M-NSC-MW, M = Fe, Zn, Co, and Ni. Among the various M-NSC-MW, Fe-NSC-MW possesses the highest ORR electrochemical activity in alkaline electrolytes. Its onset potential (Eonset) is 0.955 V, and its half-wave potential (E1/2) can reach 0.852 V, both of which are the same as those of commercial Pt/C. Moreover, Fe-NSC-MW also exhibits much superior ORR catalytic efficiency than conventional pyrolysis samples. It is worth noting that Zn-NSC–MW is prepared for the first time, and it also shows a high ORR performance with an Eonset of 0.945 V and an E1/2 of 0.832 V. This work has revealed the general application of the microwave-assisted heating method to prepare well-dispersed transition metal SACs anchored on the N,S-codoped graphene/carbon hybrid matrix.

Understanding the dynamic evolution of atomically dispersed Cu catalyst for CO2 electrochemical conversion using integrated XANES analysis and mechanistic studies

Direct electrochemical conversion of CO2 to ethanol (CH3CH2OH) offers a promising strategy to lower CO2 emission while storing energy from renewable electricity. Our recent study reported a carbon-supported atomically dispersed Cu catalyst that achieved the highest reported selectivity for CH3CH2OH formation (91%) at a relatively low potential (-0.6 V), however, the active site structure that is responsible for such high activity and selectivity has yet to be understood. In this paper, we demonstrate a computational investigation combining X-ray absorption near edge structure (XANES) simulations and a mechanistic study via density functional theory (DFT) to understand the catalyst structures of this Cu catalyst during electrocatalysis and the corresponding reaction mechanisms of the key products. An integrated computational and experimental XANES analysis depicted the dynamic evolution of the catalytic site during electrocatalysis. The as-prepared, atomically dispersed Cu catalyst aggregates and forms metallic clusters/nanoparticles under electrochemical condition, which then break down to smaller oxidized clusters after electrocatalysis. The formed Cu clusters/nanoparticles showed distinct catalytic activity and selectivity as a function of particle size based on the mechanistic investigation using DFT, which is consistent with experimental observations for catalyst samples with different Cu loadings. This comprehensive study which combines experimental and computational XANES investigation, mechanistic study via DFT calculations, and experimental performance of the catalysts, provides unprecedented dynamic and mechanistic insights into the supported atomically dispersed metal catalysts for CO2 reduction. Such strategy and details gained can further guide discovery of novel catalyst materials for CO2 electrochemical reduction.

Metal-support interaction induced atomic dispersion and redispersion of Pd on CeO2 for passive NOx adsorption

Atomically dispersed metal catalysts have attracted extensive attention in the fields of heterogeneous catalysis due to the enhanced intrinsic activity and selectivity in many energy and environment related reactions, while they suffer from sintering under harsh reaction conditions. Herein, atomically dispersed Pd/CeO2 was synthesized and investigated as a passive NOx adsorber (PNA) material. The strong interaction between CeO2 and Pd creates Pd-O-Ce linkages with 100% utilization of Pd for NOx trapping, being one of the most active oxide-based PNAs up to date. Although a sulfation treatment can substantially reduce NOx storage capacity (NSC) on the Pd/CeO2, a two-step desulfation process, including a cold plasma treatment and an oxidative calcination, can recover near 90% of its original NSC. Desulfation caused Pd aggregating into nanoparticles (NPs), while reconstruction of Pd-O-Ce moieties was achieved by prolonged oxidation at 500 °C, driving by the strong metal-support interaction between Pd and CeO2. The Pd/CeO2 system exemplifies the advantages of the metal and oxide support interaction for the atomic dispersion of Pd and redispersion of sintered Pd NPs. Monitoring this dynamic interaction enables the atomically dispersed metal structure to be modulated in controlled reaction environments, being such an example, the enhanced performance of Pd/CeO2 in PNA applications was shown in the present manuscript.

Atomically dispersed metal catalysts towards nitrogen reduction for Ammonia: From homogeneous to heterogeneous

Ammonia (NH3) is an essential chemical in agriculture and industry, which plays a crucial role in human life and sustainable development. To date, ammonia production mainly relies on the energy-intensive Haber-Bosch process, resulting in significant energy consumption and CO2 emissions. Electrocatalytic nitrogen reduction reaction (NRR) that can produce NH3 under ambient conditions is considered as a potential alternative to Haber-Bosch. However, electrocatalytic NRR has various limitations, including low ammonia yield, inferior selectivity due to competing hydrogen evolution reactions, and sluggish reaction kinetics. By virtue of maximum metal atom utilization and tunable electronic structure, atomically dispersed metal catalysts (ADMCs) offer great opportunities for NRR performance optimization, and thus being the most promising NRR catalysts. In this review, we summarize the developmental evolution of ADMCs from homogeneous to heterogeneous phases. We start with a fundamental understanding of the reaction mechanism, detection methods, and key evaluation parameters of NRR. Following this, atomically dispersed homogeneous metal catalysts, including noble metal-based, transition metal-based, and titanium chloride-based, are presented with their advantages and disadvantages analyzed in detail. To conquer the shortcomings of homogenous catalysts, heterogenous catalysts with various supports are more appealing and their recent progress is documented as well. Finally, we present the challenges and perspectives of the ADMCs catalysts for NRR, aiming to provide guidance for advanced NRR catalyst design.

Facile and Eco-Friendly Approach To Produce Confined Metal Cluster Catalysts

Zeolite-supported metal nanocluster catalysts have attracted significant attention due to their broad application in heterogeneously catalyzed reactions. The preparation of highly dispersed metal catalysts commonly involves the use of organic compounds and requires the implementation of complicated procedures, which are neither green nor deployable at the large scale. Herein, we present a novel facile method (vacuum-heating) which employs a specific thermal vacuum processing protocol of catalysts to promote the decomposition of metal precursors. The removal of coordinated H2O via vacuum-heating restricts the formation of intermediates (metal-bound OH species), resulting in catalysts with a uniform, metal nanocluster distribution. The structure of the intermediate was determined by in situ Fourier transform infrared, temperature-programmed decomposition, and X-ray absorption spectroscopy (XAS) measurements. This alternative synthesis method is eco-friendly and cost-effective as the procedure occurs in the absence of organic compounds. It can be widely used for the preparation of catalysts from different metal species (Ni, Fe, Cu, Co, Zn) and precursors and is readily scaled-up.

Inside Cover: Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts (Angew. Chem. Int. Ed. 16/2023)

The low-temperature conversion of Pd nanoclusters into Pd single atoms with the assistance of Cl ligands is illustrated by Tao Ding, Xiaokang Liu, Manzhou Zhu, Tao Yao et al. in their Research Article (e202218630). The Pd nanoclusters collapse when coordinated by Cl ligands, thus enabling the transformation to take place at low temperatures (400 °C). This study sheds light on the rational design of atomically dispersed metal catalysts.

Innentitelbild: Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts (Angew. Chem. 16/2023)

Innentitelbild: Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts (Angew. Chem. 16/2023)

Genesis of Active Pt/CeO2 Catalyst for Dry Reforming of Methane by Reduction and Aggregation of Isolated Platinum Atoms into Clusters.

Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction-driven structural evolution of a cerium oxide-supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X-ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. The results emphasize the need for in-operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate-limiting dissociation of light alkanes.

Highly Dispersed Pt Stabilized by ZnOx-Si on Self-Pillared Zeolite Nanosheets for Propane Dehydrogenation

Atomically dispersed metal catalysts can maximize the utilization of metals and provide unique chemical properties for catalytic reactions. However, the stabilities of high-loading metal clusters on solid supports are still under dispute, because small clusters are prone to agglomerate into larger particles at high temperature. Here, we prepared thermally stable highly dispersed Pt species immobilized by bridging Zn2+ sites and silanol groups (Si-OH) on self-pillared silicalite-1 zeolite nanosheets (SP-S-1). The rotationally overgrown zeolite sheet-like structure provided a high specific surface area and abundant Si-OH, which favored atomically dispersed active sites with ZnOx-Si nanoclusters. The as-prepared PtZn/SP-S-1 exhibited a high specific activity of 1.23 molC3H6·gcatal–1·h–1 at 580 °C with propylene selectivity up to 99%. Moreover, no obvious deactivation was observed after 90 h on stream under a weight hourly space velocity of 15 h–1. The self-pillared nanosheet-supported metal catalysts provide prospective guidance for high-temperature catalysis.

Electrocatalysis of Selective Chlorine Evolution Reaction: Fundamental Understanding and Catalyst Design

<p>The electrochemical chlorine evolution reaction (CER) is an important electrochemical reaction and has been widely used in chlor–alkali electrolysis, on-site generation of ClO<sup>−</sup>, and Cl<sub>2</sub>-mediated electrosynthesis. Although precious metal-based mixed metal oxides (MMOs) have been used as CER catalysts for more than half a century, they intrinsically suffer from a selectivity problem between the CER and parasitic oxygen evolution reaction (OER). Hence, the design of selective CER electrocatalysts is critically important. In this review, we provide an overview of the fundamental issues related to the electrocatalysis of the CER and design strategies for selective CER electrocatalysts. We present experimental and theoretical methods for assessing the active sites of MMO catalysts and the origin of the scaling relationship between the CER and the OER. We discuss kinetic analysis methods to understand the kinetics and mechanisms of CER. Next, we summarize the design strategies for new CER electrocatalysts that can enhance the reactivity of MMO-based catalysts and overcome their scaling relationship, which include the doping of MMO catalysts with foreign metals and the development of non-precious metal-based catalysts and atomically dispersed metal catalysts.</p>

Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts

AbstractThe transformation from metal nanocluster catalysts to metal single‐atom catalysts is an important procedure in the rational design of atomically dispersed metal catalysts (ADCs). However, the conversion methods often involve high annealing temperature as well as reducing atmosphere. Herein, we reported a continuous and convenient approach to transfer Pd nanocluster into Pd single‐atom in a ligand assisted annealing procedure, by which means we reduced its activating temperature low to 400 °C. Using ex‐situ microscopy and spectroscopy, we comprehensively monitored the structural evolution of Pd species though the whole atomization process. Theoretical calculation revealed that the structural instability caused by remaining Cl ligands was the main reason for this low‐temperature transformation. The present atomization strategy and mechanistic knowledge for the conversion from cluster to atomic dispersion provides guidelines for the rational design of ADCs.

Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts.

The transformation from metal nanocluster catalysts to metal single-atom catalysts is an important procedure in the rational design of atomically dispersed metal catalysts (ADCs). However, the conversion methods often involve high annealing temperature as well as reducing atmosphere. Herein, we reported a continuous and convenient approach to transfer Pd nanocluster into Pd single-atom in a ligand assisted annealing procedure, by which means we reduced its activating temperature low to 400 °C. Using ex-situ microscopy and spectroscopy, we comprehensively monitored the structural evolution of Pd species though the whole atomization process. Theoretical calculation revealed that the structural instability caused by remaining Cl ligands was the main reason for this low-temperature transformation. The present atomization strategy and mechanistic knowledge for the conversion from cluster to atomic dispersion provides guidelines for the rational design of ADCs.

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance.

Atomically dispersed metal catalysts show potential advantages in N2 reduction reaction (NRR) due to their excellent activity and efficient metal utilization. Unfortunately, the reported catalysts usually exhibit unsatisfactory NRR activity due to their poor N2 adsorption and activation. Herein, we report a novel Sn atomically dispersed protuberance (ADP) by coordination with substrate C and O to induce positive charge accumulation on Sn site for improving its N2 adsorption, activation and NRR performance. The extended X-ray absorption fine structure (EXAFS) spectra confirmed the local coordination structure of the Sn ADPs. NRR activity was significantly promoted via Sn ADPs, exhibiting a remarkable NH3 yield (RNH3 ) of 28.3 μg h-1 mgcat -1 (7447 μg h-1 mgSn -1 ) at -0.3 V. Furthermore, the enhanced N2 Hx intermediates was verified by in situ experiments, yielding consistent results with DFT calculation. This work opens a new avenue to regulate the activity and selectivity of N2 fixation.

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance

AbstractAtomically dispersed metal catalysts show potential advantages in N2 reduction reaction (NRR) due to their excellent activity and efficient metal utilization. Unfortunately, the reported catalysts usually exhibit unsatisfactory NRR activity due to their poor N2 adsorption and activation. Herein, we report a novel Sn atomically dispersed protuberance (ADP) by coordination with substrate C and O to induce positive charge accumulation on Sn site for improving its N2 adsorption, activation and NRR performance. The extended X‐ray absorption fine structure (EXAFS) spectra confirmed the local coordination structure of the Sn ADPs. NRR activity was significantly promoted via Sn ADPs, exhibiting a remarkable NH3 yield (RNH3) of 28.3 μg h−1 mgcat−1 (7447 μg h−1 mgSn−1) at −0.3 V. Furthermore, the enhanced N2Hx intermediates was verified by in situ experiments, yielding consistent results with DFT calculation. This work opens a new avenue to regulate the activity and selectivity of N2 fixation.

Atomically Dispersed Metals on Nanodiamond-Derived Hybrid Materials for Heterogeneous Catalysis

ConspectusSupported metal catalyst, has been one of the most important systems in the field of heterogeneous catalysis. The great complexity of both the compositions and structures of such supported metal catalysts provides a great degree of freedom for tuning their catalytic properties, which has essentially triggered the explosive growth in research on design and control active metals’ surface structures for decades. An ideal metal catalyst theoretically features maximum active sites and optimal intrinsic reactivity to facilitate a desired chemical reaction. Inspired by the catalytic concepts brought by natural enzymes and homogeneous catalysis, the fabrication of heterogeneous catalysts with atomically dispersed metal atoms has attracted much attention and been extensively explored in recent years.Atomically dispersed metal catalysts (ADMCs) including single-atom catalyst (SACs) and fully exposed cluster catalyst (FECCs), as shining stars in heterogeneous catalysts have recently drawn much attention. The advantages of ADMCs mainly include the following three aspects: (1) the fully exposed active metal atoms can realize the utmost atomic utilization efficiency and reduce the cost of catalysts; (2) the geometric and electronic structure can be effectively regulated by altering the coordination environments of metal atoms and then further tuning the catalytic performance in terms of activity, selectivity, and stability; (3) the precisely designed structures provide a promising platform for digging the structure–performance relationships of active sites with the assistance of theoretical calculations. Owing to these advantages, ADMCs have been used in thermal-catalysis, electrocatalysis, photocatalysis, etc. until now.In this Account, a summary of recent progress regarding ADMCs for heterogeneous thermal catalysis in our group will be presented from the following aspects. First, an overview of great opportunities brought by nanodiamond and its derivatives as substrates for anchoring atomically dispersed metals (ADMs) and tailoring their structures. Next, our recent progress in achieving desirable catalytic performance, including activity, selectivity, and stability over nanodiamond–graphene (ND@G) supported ADMCs will be introduced in detail. Finally, a brief outlook regarding the development directions for ADMCs by discussing current challenges and opportunities will be proposed. It is hoped that this Account can inspire the development of the rational design and various application of ADMCs.

Impact of catalyst loading of atomically dispersed transition metal catalysts on H2O2 electrosynthesis selectivity

Electrosynthesis of hydrogen peroxide (H2O2) via a two-electron oxygen reduction reaction (2e− ORR) has emerged as a promising alternative to the current anthraquinone process. Atomically dispersed transition metal catalysts (M–N/C catalysts; M=transition metal) have received particular attention as H2O2 electrosynthesis catalysts. Among the factors affecting catalytic properties, the catalyst loading on the electrode has significant impacts on the ORR activity and selectivity of M–N/C catalysts in particular and electrocatalysts in general. However, the loading effect has been largely neglected and underexplored in literature. In this study, we investigated the impacts of the catalyst loading and the metal center in M–N/C catalysts on the 2e− ORR activity and selectivity. We prepared a series of mesoporous carbons comprising M (Fe, Co, Ni)-based atomically dispersed species, meso‑M–N/C catalysts. At a fixed low catalyst loading, the meso‑Co–N/C and meso‑Ni–N/C catalysts exhibited the best 2e−ORR performance under acidic and alkaline electrolytes, respectively. At high catalyst loadings, the H2O2 production activity of the meso‑Co–N/C catalyst dramatically declined to ∼20% compared to that at the low loading. In the thick catalyst layer, the generated H2O2 is accumulated due to poor mass transport, leading to reduction and/or decomposition. In contrast, the H2O2 synthesis activity meso‑Ni–N/C catalyst was nearly insensitive to the catalyst loading, which can be ascribed to the high porosity and well-developed mesopores of the meso‑Ni–N/C catalyst, promoting mass transport.