Unveiling the Role of Cationic Pyridine Sites in Covalent Triazine Framework for Boosting Zinc-Iodine Batteries Performance.

Rechargeable Zinc-iodine batteries (ZIBs) are gaining attention as energy storage devices due to their high energy density, low-cost, and inherent safety. However, the poor cycling performance of these batteries always arises from the severe leakage and shuttle effect of polyiodides (I3 - and I5 -). Herein, a novel cationic pyridine-rich covalent triazine framework (CCTF-TPMB) is developed to capture and confine iodine (I2) species via strong electrostatic interaction, making it an attractive host for I2 in ZIBs. The as-fabricated ZIBs with I2 loaded CCTF-TPMB (I2@CCTF-TPMB) cathode achieve a large specific capacity of 243 mAh g-1 at 0.2 A g-1 and an exceptionally stable cyclic performance, retaining 93.9% of its capacity over 30 000 cycles at 5 A g-1. The excellent electrochemical performance of the ZIBs can be attributed to the pyridine-rich cationic sites of CCTF-TPMB, which effectively suppress the leakage and shuttle of polyiodides, while also accelerating the conversion reaction of I2 species. Combined in situ Raman and UV-vis analysis, along with theoretical calculations, clearly reveal the critical role played by pyridine-rich cationic sites in boosting the ZIBs performances. This work opens up a promising pathway for designing advanced I2 cathode materials toward next-generation ZIBs and beyond.

PtPd Atomic Layer Shelled PdCu Hollow Nanoparticles on Partially Unzipped Carbon Nanotubes for Breaking the Activity-Stability Trade-Off toward the Hydrogen Oxidation Reaction in Alkaline Media.

Developing highly active yet stable catalysts for the hydrogen oxidation reaction (HOR) in alkaline media remains a significant challenge. Herein, we designed a novel catalyst of atomic PtPd-layer shelled ultrasmall PdCu hollow nanoparticles (HPdCu NPs) on partially unzipped carbon nanotubes (PtPd@HPdCu/W-CNTs), which can achieve a high mass activity, 5 times that of the benchmark Pt/C, and show exceptional stability with negligible decay after 20,000 cycles of accelerated degradation test. The atomically thin PtPd shell serves as the primary active site for the HOR and a protective layer that prevents Cu leaching. Additionally, the HPdCu substrate not only tunes the adsorption properties of the PtPd layer but also prevents corrosive Pt from reaching the interface between NPs and the carbon support, thereby mitigating carbon corrosion. This work introduces a new strategy that leverages the distinct advantages of multiple components to address the challenges associated with slow kinetics and poor durability toward the HOR.

Ligand-engineering Cu-based catalysts to accelerate the electrochemical reduction of CO2.

Two typical Cu-based complex catalysts with piperazine (PR) and p-phenylenediamine (pPDA) ligands were designed to elucidate whether the ligands can tailor the reduction behavior of the Cu species and thus modulate their electrochemical CO2 reduction reaction (eCO2RR) activity. Specifically, Cu-PR underwent a significant in situ transformation into Cu nanoparticles enriched with a Cuδ+/Cu0 interface for high eCO2RR activity, compared to Cu-pPDA. This finding reveals the importance of ligand engineering in modulating the eCO2RR performance of Cu-based complexes.

Sulfur-bridge ligands altering the microenvironment of single-atom CoN3S sites to boost the oxygen reduction reaction.

We report here an asymmetric N,S-coordinated cobalt-based single-atom catalyst with sulfur (S)-bridge ligands (Co-N/S-C) for the oxygen reduction reaction (ORR). The Co-N/S-C exhibits a half-wave potential (E1/2) of 0.908 V versus RHE, outperforming most state-of-the-art ORR catalysts. Theoretical calculations indicate that the CoN3SC10-S moiety facilitates the ORR kinetics by optimizing the adsorption of intermediates. This work provides new insights into the design of single-atom catalysts for electrocatalysis through heteroatom-bridge ligand engineering.

Stable and High-performance Flow H2-O2 Fuel Cells with Coupled Acidic Oxygen Reduction and Alkaline Hydrogen Oxidation Reactions.

Conventional H2-O2 fuel cells suffer from the low output voltage, insufficient durability, and high-cost catalysts (e.g., noble metals). Herein, this work reports a conceptually new coupled flow fuel cell (CF-FC) by coupling asymmetric electrolytes for acidic oxygen reduction reaction and alkaline hydrogen oxidation reaction. By introducing an electrochemical neutralization energy, the newly-developed CF-FCs possess a significantly increased theoretical open-circuit voltage. Specifically, a CF-FC based on a typical transition metal single-atom Fe-N-C cathode catalyst demonstrates a high electricity output up to 1.81 V and durability with an ultrahigh retention of 91% over 110 h, far superior to the conventional fuel cells (usually, < 1.0 V, < 50% retention over 20 h). The output performance can even be significantly enhanced easily by connecting multiple CF-FCs into the parallel, series, or combined parallel-series connections at a fractional cost of that for the conventional H2-O2 fuel cells, showing great potential for large-scale practical applications. Thus, this study provides a platform to transform conventional fuel cell technology through the rational design and development of advanced energy conversion and storage devices by coupling different electrocatalytic reactions.

A universal approach to dual-metal-atom catalytic sites confined in carbon dots for various target reactions.

Here, a molecular-design and carbon dot-confinement coupling strategy through the pyrolysis of bimetallic complex of diethylenetriamine pentaacetic acid under low-temperature is proposed as a universal approach to dual-metal-atom sites in carbon dots (DMASs-CDs). CDs as the "carbon islands" could block the migration of DMASs across "islands" to achieve dynamic stability. More than twenty DMASs-CDs with specific compositions of DMASs (pairwise combinations among Fe, Co, Ni, Mn, Zn, Cu, and Mo) have been synthesized successfully. Thereafter, high intrinsic activity is observed for the probe reaction of urea oxidation on NiMn-CDs. In situ and ex situ spectroscopic characterization and first-principle calculations unveil that the synergistic effect in NiMn-DMASs could stretch the urea molecule and weaken the N-H bond, endowing NiMn-CDs with a low energy barrier for urea dehydrogenation. Moreover, DMASs-CDs for various target electrochemical reactions, including but not limited to urea oxidation, are realized by optimizing the specific DMAS combination in CDs.

Tailoring the Atomic-Local Environment of Carbon Nanotube Tips for Selective H2 O2 Electrosynthesis at High Current Densities.

The atomic-local environment of catalytically active sites plays an important role in tuning the activity of carbon-based metal-free electrocatalysts (C-MFECs). However, the rational regulation of the environment is always impeded by synthetic limitations and insufficient understanding of the formation mechanism of the catalytic sites. Herein, the possible cleavage mechanism of carbon nanotubes (CNTs) through the crossing points during ball-milling is proposed, resulting in abundant CNT tips that are more susceptible to be modified by heteroatoms, achieving precise modulation of the atomic environment at the tips. The obtained CNTs with N,S-rich tips (N,S-TCNTs) exhibit a wide potential window of 0.59 V along with H2 O2 selectivity for over 90.0%. Even using air as the O2 source, the flow cell system with N,S-TCNTs catalyst attains high H2 O2 productivity up to 30.37 mol gcat. -1  h-1 @350 mA cm-2 , superior to most reported C-MFECs. From a practical point of view, a solid electrolyzer based on N,S-TCNTs is further employed to realize the in-situ continuous generation of pure H2 O2 solution with high productivity (up to 4.35 mmol cm-2  h-1 @300 mA cm-2 ; over 300 h). The CNTs with functionalized tips hold great promise for practical applications, even beyond H2 O2 generation.

Fe/Co dual metal catalysts modulated by S-ligands for efficient acidic oxygen reduction in PEMFC.

Here, we report a conceptual strategy for introducing spatial sulfur (S)-bridge ligands to regulate the coordination environment of Fe-Co-N dual-metal centers (Spa-S-Fe,Co/NC). Benefiting from the electronic modulation, Spa-S-Fe,Co/NC catalyst showed remarkably enhanced oxygen reduction reaction (ORR) performance with a half-wave potential (E1/2) of 0.846 V and satisfactory long-term durability in acidic electrolyte. Combined experimental and theoretical studies revealed that the excellent acidic ORR activity with a remarkable stability observed for Spa-S-Fe,Co/NC is attributable to the optimal adsorption-desorption of ORR oxygenated intermediates achieved through charge-modulation of Fe-Co-N bimetallic centers by the spatial S-bridge ligands. These findings provide a unique perspective to regulate the local coordination environment of catalysts with dual-metal-centers to optimize their electrocatalytic performance.

The role of oxygen-vacancy in bifunctional indium oxyhydroxide catalysts for electrochemical coupling of biomass valorization with CO2 conversion.

Electrochemical coupling of biomass valorization with carbon dioxide (CO2) conversion provides a promising approach to generate value-added chemicals on both sides of the electrolyzer. Herein, oxygen-vacancy-rich indium oxyhydroxide (InOOH-OV) is developed as a bifunctional catalyst for CO2 reduction to formate and 5-hydroxymethylfurfural electrooxidation to 2,5-furandicarboxylic acid with faradaic efficiencies for both over 90.0% at optimized potentials. Atomic-scale electron microscopy images and density functional theory calculations reveal that the introduction of oxygen vacancy sites causes lattice distortion and charge redistribution. Operando Raman spectra indicate oxygen vacancies could protect the InOOH-OV from being further reduced during CO2 conversion and increase the adsorption competitiveness for 5-hydroxymethylfurfural over hydroxide ions in alkaline electrolytes, making InOOH-OV a main-group p-block metal oxide electrocatalyst with bifunctional activities. Based on the catalytic performance of InOOH-OV, a pH-asymmetric integrated cell is fabricated by combining the CO2 reduction and 5-hydroxymethylfurfural oxidation together in a single electrochemical cell to produce 2,5-furandicarboxylic acid and formate with high yields (both around 90.0%), providing a promising approach to generate valuable commodity chemicals simultaneously on both electrodes.

Physicochemical Dual Cross-Linking Conductive Polymeric Networks Combining High Strength and High Toughness Enable Stable Operation of Silicon Microparticle Anodes.

The poor interfacial stability and insufficient cycling performance caused by undesirable stress hinder the commercial application of silicon microparticles (µSi) as next-generation anode materials for high-energy-density lithium-ion batteries. Herein, a conceptionally novel physicochemical dual cross-linking conductive polymeric network is designed combining high strength and high toughness by coupling the stiffness of poly(acrylic acid) and the softness of carboxyl nitrile rubber, which includes multiple H-bonds, by introducing highly branched tannic acid as a physical cross-linker. Such a design enables effective stress dissipation by folded molecular chains slipping and sequential cleavage of H-bonds, thus stabilizing the electrode interface and enhancing cycle stability. As expected, the resultant electrode (µSi/PTBR) delivers an unprecedented high capacity retention of ≈97% from 2027.9 mAh g-1 at the 19th to 1968.0 mAh g-1 at the 200th cycle at 2 A g-1 . Meanwhile, this unique stress dissipation strategy is also suitable for stabilizing SiOx anodes with a much lower capacity loss of ≈0.012% per cycle over 1000 cycles at 1.5 A g-1 . Atomic force microscopy analysis and finite element simulations reveal the excellent stress-distribution ability of the physicochemical dual cross-linking conductive polymeric network. This work provides an efficient energy-dissipation strategy toward practical high-capacity anodes for energy-dense batteries.

Carbon-Based Electrocatalysts for Acidic Oxygen Reduction Reaction.

Oxygen reduction reaction (ORR) is vital for clean and renewable energy technologies, which require no fossil fuel but catalysts. Platinum (Pt) is the best-known catalyst for ORR. However, its high cost and scarcity have severely hindered renewable energy devices (e.g., fuel cells) for large-scale applications. Recent breakthroughs in carbon-based metal-free electrochemical catalysts (C-MFECs) show great potential for earth-abundant carbon materials as low-cost metal-free electrocatalysts towards ORR in acidic media. This article provides a focused, but critical review on C-MFECs for ORR in acidic media with an emphasis on advances in the structure design and synthesis, fundamental understanding of the structure-property relationship and electrocatalytic mechanisms, and their applications in proton exchange membrane fuel cells. Current challenges and future perspectives in this emerging field are also discussed.

Label-free electrochemical immunosensor for highly sensitive COVID-19 spike protein detection.

The ongoing coronavirus pandemic responsible for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has rapidly increased the rate of global death and infections due to variant mutations (such as Delta and Omicron). While specifically developed and approved vaccines can limit the spread of disease in a population and severity of resulting symptoms, none have been demonstrated to effectively prevent infection altogether. Thus, reliable early diagnosis of COVID-19 is critical to identify positive cases to help contain the outbreak. Herein we report a label-free electrochemical immunosensor for rapid diagnosis of COVID-19 by using nitrogen-doped holey graphene (N-HRGO) as a nanocarrier decorated with thionine (TH) molecules as electrochemical indicators. With the spike protein located on the surface of the COVID-19 particles as the model target, the as-prepared electrochemical immunosensor could detect the presence of the COVID-19 spike protein over a wide linear range (1 pg mL-1-10 ng mL-1) with a low detection limit (0.3 pg mL-1). In addition, the developed electrochemical immunosensor exhibited an excellent selectivity (with insignificant current changes towards interfering proteins comparing with COVID-19 spike protein), a good reproducibility and long-term storage stability. Importantly, the electrochemical immunosensor thus developed could successfully and reliably detect the spike protein of COVID-19 in saliva and human serum complex samples. Thus, the as-prepared label-free electrochemical immunosensor can achieve rapid and sensitive detection of the COVID-19 spike protein, as a promising clinical diagnosis tool in monitoring the progression of COVID-19.

Understanding of catalytic ROS generation from defect-rich graphene quantum-dots for therapeutic effects in tumor microenvironment.

Owing to their low cost, high catalytic efficiency and biocompatibility, carbon-based metal-free catalysts (C-MFCs) have attracted intense interest for various applications, ranging from energy through environmental to biomedical technologies. While considerable effort and progress have been made in mechanistic understanding of C-MFCs for non-biomedical applications, their catalytic mechanism for therapeutic effects has rarely been investigated. In this study, defect-rich graphene quantum dots (GQDs) were developed as C-MFCs for efficient ROS generation, specifically in the H2O2-rich tumor microenvironment to cause multi-level damages of subcellular components (even in nuclei). While a desirable anti-cancer performance was achieved, the catalytic performance was found to strongly depend on the defect density. It is for the first time that the defect-induced catalytic generation of ROS by C-MFCs in the tumor microenvironment was demonstrated and the associated catalytic mechanism was elucidated. This work opens a new avenue for the development of safe and efficient catalytic nanomedicine.

Carbon-based metal-free electrocatalysts: from oxygen reduction to multifunctional electrocatalysis.

Since the discovery of N-doped carbon nanotubes as the first carbon-based metal-free electrocatalyst (C-MFEC) for oxygen reduction reaction (ORR) in 2009, C-MFECs have shown multifunctional electrocatalytic activities for many reactions beyond ORR, such as oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR), and hydrogen peroxide production reaction (H2O2PR). Consequently, C-MFECs have attracted a great deal of interest for various applications, including metal-air batteries, water splitting devices, regenerative fuel cells, solar cells, fuel and chemical production, water purification, to mention a few. By altering the electronic configuration and/or modulating their spin angular momentum, both heteroatom(s) doping and structural defects (e.g., atomic vacancy, edge) have been demonstrated to create catalytic active sites in the skeleton of graphitic carbon materials. Although certain C-MFECs have been made to be comparable to or even better than their counterparts based on noble metals, transition metals and/or their hybrids, further research and development are necessary in order to translate C-MFECs for practical applications. In this article, we present a timely and comprehensive, but critical, review on recent advancements in the field of C-MFECs within the past five years or so by discussing various types of electrocatalytic reactions catalyzed by C-MFECs. An emphasis is given to potential applications of C-MFECs for energy conversion and storage. The structure-property relationship for and mechanistic understanding of C-MFECs will also be discussed, along with the current challenges and future perspectives.

Carbon-Defect-Driven Electroless Deposition of Pt Atomic Clusters for Highly Efficient Hydrogen Evolution.

Pt atomic clusters (Pt-ACs) display outstanding electrocatalytic performance because of their unique electronic structure with a large number of highly exposed surface atoms. However, the small size and large specific surface area intrinsically associated with ACs pose challenges in the synthesis and stabilization of Pt-ACs without agglomeration. Herein, we report a novel one-step carbon-defect-driven electroless deposition method to produce ultrasmall but well-defined and stable Pt-ACs supported by defective graphene (Pt-AC/DG) structures. A theoretical simulation clearly revealed that the defective regions with a lower work function and hence a higher reducing capacity compared to those of normal hexagonal sites triggered the reduction of Pt ions preferentially at the defect sites. Moreover, the strong binding energy between Pt and carbon defects effectively restricted the migration of spontaneously reduced Pt atoms to immobilize/stabilize the resultant Pt-ACs. Electrochemical analyses demonstrated the high performance of Pt-ACs in catalyzing the hydrogen evolution reaction, showing a greatly enhanced mass activity, a high Pt utilization efficiency, and excellent stability compared with commercial Pt/C catalysts. The integration of proton exchange membrane water electrolysis with Pt-AC/DG as a cathode exhibited an excellent hydrogen generation activity and extraordinary stability (during 200 h of electrolysis) with a greatly reduced Pt usage compared with commercial Pt/C catalysts.

High-Performance, Long-Life, Rechargeable Li-CO2 Batteries based on a 3D Holey Graphene Cathode Implanted with Single Iron Atoms.

A highly efficient cathode catalyst for rechargeable Li-CO2 batteries is successfully synthesized by implanting single iron atoms into 3D porous carbon architectures, consisting of interconnected N,S-codoped holey graphene (HG) sheets. The unique porous 3D hierarchical architecture of the catalyst with a large surface area and sufficient space within the interconnected HG framework can not only facilitate electron transport and CO2 /Li+ diffusion, but also allow for a high uptake of Li2 CO3 to ensure a high capacity. Consequently, the resultant rechargeable Li-CO2 batteries exhibit a low potential gap of ≈1.17 V at 100 mA g-1 and can be repeatedly charged and discharged for over 200 cycles with a cut-off capacity of 1000 mAh g-1 at a high current density of 1 A g-1 . Density functional theory calculations are performed and the observed appealing catalytic performance is correlated with the hierarchical structure of the carbon catalyst. This work provides an effective approach to the development of highly efficient cathode catalysts for metal-CO2 batteries and beyond.

High-Performance K-CO2 Batteries Based on Metal-Free Carbon Electrocatalysts.

Metal-CO2 batteries have attracted much attention owing to their high energy density and use of greenhouse CO2 waste as the energy source. However, the increasing cost of lithium and the low discharge potential of Na-CO2 batteries create obstacles for practical applications of Li/Na-CO2 batteries. Recently, earth-abundant potassium ions have attracted considerable interest as fast ionic charge carriers for electrochemical energy storage. Herein, we report the first K-CO2 battery with a carbon-based metal-free electrocatalyst. The battery shows a higher theoretical discharge potential (E⊖ =2.48 V) than that of Na-CO2 batteries (E⊖ =2.35 V) and can operate for more than 250 cycles (1500 h) with a cutoff capacity of 300 mA h g-1 . Combined DFT calculations and experimental observations revealed a reaction mechanism involving the reversible formation and decomposition of P121 /c1-type K2 CO3 at the efficient carbon-based catalyst.

Carbon Nanomaterials for Energy and Biorelated Catalysis: Recent Advances and Looking Forward.

Along with the wide investigation activities in developing carbon-based, metal-free catalysts to replace precious metal (e.g., Pt) catalysts for various green energy devices, carbon nanomaterials have also shown great potential for biorelated applications. This article provides a focused, critical review on the recent advances in these emerging research areas. The structure-property relationship and mechanistic understanding of recently developed carbon-based, metal-free catalysts for chemical/biocatalytic reactions will be discussed along with the challenges and perspectives in this exciting field, providing a look forward for the rational design and fabrication of new carbon-based, metal-free catalysts with high activities, remarkable selectivity, and outstanding durability for various energy-related/biocatalytic processes.

Carbon-Based Metal-Free Catalysts for Energy Storage and Environmental Remediation.

Owing to their high earth-abundance, eco-friendliness, high electrical conductivity, large surface area, structure tunability at the atomic/morphological levels, and excellent stability in harsh conditions, carbon-based metal-free materials have become promising advanced electrode materials for high-performance pseudocapacitors and metal-air batteries. Furthermore, carbon-based nanomaterials with well-defined structures can function as green catalysts because of their efficiency in advanced oxidation processes to remove organics in air or from water, which reduces the cost for air/water purification and avoids cross-contamination by eliminating the release of heavy metals/metal ions. Here, the research and development of carbon-based catalysts in supercapacitors and batteries for clean energy storage as well as in air/water treatments for environmental remediation are reviewed. The related mechanistic understanding and design principles of carbon-based metal-free catalysts are illustrated, along with the challenges and perspectives in this emerging field.

Doping of Carbon Materials for Metal-Free Electrocatalysis.

Carbon atoms in the graphitic carbon skeleton can be replaced by heteroatoms with different electronegative from that of the carbon atom (i.e., heteroatom doping) to modulate the charge distribution over the carbon network. The charge modulation can be achieved via direct charge transfer with an electron acceptor/donor (i.e., charge transfer doping) or through introduction of defects (i.e., defective doping). Various doping strategies, including heteroatom doping, charge-transfer doping, and defective doping, have now been devised for modulating the charge distribution of numerous graphite carbon materials to impart new properties to carbon materials. Consequently, carbon nanomaterials with defined doping have recently become prominent members in the carbon family, promising for a variety of applications, including catalysis, energy conversion and storage, environmental remediation, and important chemical production and industrial processes. The purpose of this review is to present an overview on the doping of carbon materials for metal-free electrocatalysis, especially the development of doping strategies and doping-induced structure and property changes for potential catalytic applications. Current challenges and future perspectives in the doped carbon-based metal-free catalyst field are also discussed.