Surface Modification of a Lignin-Derived Carbon-Supported Co-Based Metal/Oxide Nanostructure for Alkaline Water Splitting

Exploring low-cost and eco-friendly bifunctional electrocatalysts of the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline electrolytes is still highly desired, and is crucial for water electrolysis and sustainable hydrogen generation. In this work, we report a facile pyrolysis–oxidation strategy to convert by-product lignin into bifunctional OER/HER electrocatalysts (Co/Co3O4-NPC-400) composed of Co/Co3O4 anchored on N-doped carbon with a surface of rich oxygen vacancies and oxygen-containing groups. The co-pyrolysis of lignin and NH4Cl can achieve a N-doped carbon matrix with a hierarchical pore structure, while the air-annealing process can induce the formation of oxygen-containing groups and oxygen vacancies. Owing to its surface properties, hierarchical pore structure and multiple active components, the constructed Co/Co3O4-NPC-400 possesses bifunctional catalytic activity and superior stability for OER/HER, especially for unexpected OER activity with a high current density of about 320 mA∙cm−2 at a potential of 1.8 V (vs. RHE). Water electrolysis using Co/Co3O4-NPC-400 as both the anode and the cathode needs a cell voltage of 1.95 and 2.5 V to attain about 10 and 400 mA∙cm−2 in 1 M KOH. This work not only provides a general strategy for the preparation of carbon-supported electrocatalysts for water splitting, but also opens up a new avenue for the utilization of lignin.

[1]  A. Boretti.  Which thermochemical water-splitting cycle is more suitable for high-temperature concentrated solar energy? , 2022, International Journal of Hydrogen Energy.

[2]  L. Ci,et al.  Commercial carbon cloth: an emerging substrate for practical lithium metal batteries , 2022, Energy Storage Materials.

[3]  Kaitian Zheng,et al.  Engineering Crystalline Comp-Decorated (M = Mn, Fe, Ni, Cu, Zn) Amorphous Com Ldh for High-Rate Alkaline Water Splitting , 2022, SSRN Electronic Journal.

[4]  Yang Hou,et al.  Accelerated Water Dissociation Kinetics By Electron‐Enriched Cobalt Sites for Efficient Alkaline Hydrogen Evolution , 2021, Advanced Functional Materials.

[5]  Guifeng Liu,et al.  Recent advances in lignin-based porous materials for pollutants removal from wastewater. , 2021, International journal of biological macromolecules.

[6]  A. Vomiero,et al.  NiMoO4@Co3O4 Core–Shell Nanorods: In Situ Catalyst Reconstruction toward High Efficiency Oxygen Evolution Reaction , 2021, Advanced Energy Materials.

[7]  Yijun Zhong,et al.  Trifunctional electrocatalyst of N-doped graphitic carbon nanosheets encapsulated with CoFe alloy nanocrystals: the key roles of bimetal components and high-content graphitic-N , 2021 .

[8]  Jingquan Liu,et al.  Advantageous metal-atom-escape towards super-hydrophilic interfaces assembly for efficient overall water splitting , 2021, Journal of Power Sources.

[9]  Bing Zhang,et al.  Self-supported Co/CoO anchored on N-doped carbon composite as bifunctional electrocatalyst for efficient overall water splitting , 2021 .

[10]  Kangli Wang,et al.  In situ coupling of NiFe nanoparticles with N-doped carbon nanofibers for Zn-air batteries driven water splitting , 2021 .

[11]  W. Lo,et al.  In situ XPS investigation of the X-ray-triggered decomposition of perovskites in ultrahigh vacuum condition , 2021, npj Materials Degradation.

[12]  Minghua Chen,et al.  Oxygen-rich hierarchical porous carbon derived from biomass waste-kapok flower for supercapacitor electrode , 2021 .

[13]  Tianyi Kou,et al.  Perspective on High-Rate Alkaline Water Splitting , 2021 .

[14]  Heng Wang,et al.  CoOx/CoNy nanoparticles encapsulated carbon-nitride nanosheets as an efficiently trifunctional electrocatalyst for overall water splitting and Zn-air battery , 2020 .

[15]  Jia Liu,et al.  Water Dissociation Kinetic‐Oriented Design of Nickel Sulfides via Tailored Dual Sites for Efficient Alkaline Hydrogen Evolution , 2020, Advanced Functional Materials.

[16]  M. Cao,et al.  Assembling 3D flower-like Co3O4-MWCNT architecture for optimizing low-frequency microwave absorption , 2020 .

[17]  S. Kelley,et al.  Techno‐economic analysis of sugar production from lignocellulosic biomass with utilization of hemicellulose and lignin for high‐value co‐products , 2020, Biofuels, Bioproducts and Biorefining.

[18]  Xiaojun Zhao,et al.  ZIF-L-Co@carbon fiber paper composite derived Co/Co3O4@C electrocatalyst for ORR in alkali/acidic media and overall seawater splitting , 2020 .

[19]  Yangyang Song,et al.  In situ construction of Co/Co3O4 with N-doped porous carbon as a bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions , 2020 .

[20]  Jongwoo Lim,et al.  A Review of Carbon‐Supported Nonprecious Metals as Energy‐Related Electrocatalysts , 2020 .

[21]  H. Duan,et al.  Operando Identification of the Dynamic Behavior of Oxygen Vacancy-rich Co3O4 for Oxygen Evolution Reaction. , 2020, Journal of the American Chemical Society.

[22]  Jianjun Li,et al.  Periodic Three-Dimensional Nitrogen-Doped Mesoporous Carbon Spheres Embedded with Co/Co3O4 Nanoparticles toward Microwave Absorption. , 2020, ACS applied materials & interfaces.

[23]  Mengfan Wang,et al.  Pyridinic and graphitic nitrogen-enriched carbon paper as a highly active bifunctional catalyst for Zn-air batteries , 2020 .

[24]  Chenghao Yang,et al.  Synthesis of the electrochemically stable sulfur-doped bamboo charcoal as the anode material of potassium-ion batteries , 2020 .

[25]  Lin Zhou,et al.  Integrating Rh Species with NiFe Layered-Double-Hydroxide for Overall Water Splitting. , 2019, Nano letters.

[26]  Yadong Li,et al.  Synergistically Interactive Pyridinic‐N–MoP Sites: Identified Active Centers for Enhanced Hydrogen Evolution in Alkaline Solution , 2019, Angewandte Chemie.

[27]  G. Patzke,et al.  Transition metal electrocatalysts encapsulated into N-doped carbon nanotubes on reduced graphene oxide nanosheets: efficient water splitting through synergistic effects , 2019, Journal of Materials Chemistry A.

[28]  Dongyun Chen,et al.  Hollow Mesoporous Co3 O4 -CeO2 Composite Nanotubes with Open Ends for Efficient Catalytic CO Oxidation. , 2019, ChemSusChem.

[29]  Xiaobo Ji,et al.  Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER , 2019, Energy & Environmental Science.

[30]  Lishan Peng,et al.  Recent developments in metal phosphide and sulfide electrocatalysts for oxygen evolution reaction , 2018, Chinese Journal of Catalysis.

[31]  Xiaodong Chen,et al.  Multi-Level Architecture Optimization of MOF-Templated Co-Based Nanoparticles Embedded in Hollow N-Doped Carbon Polyhedra for Efficient OER and ORR , 2018, ACS Catalysis.

[32]  S. Hirano,et al.  Engineering the Interfaces of Superadsorbing Graphene-Based Electrodes with Gas and Electrolyte to Boost Gas Evolution and Activation Reactions. , 2018, ChemSusChem.

[33]  R. Basu,et al.  Multifunctional nanostructured electrocatalysts for energy conversion and storage: current status and perspectives. , 2018, Nanoscale.

[34]  M. Zheng,et al.  A nitrogen-doped nano carbon dodecahedron with Co@Co3O4 implants as a bi-functional electrocatalyst for efficient overall water splitting , 2017 .

[35]  Zhonghua Zhu,et al.  Ultrathin Iron‐Cobalt Oxide Nanosheets with Abundant Oxygen Vacancies for the Oxygen Evolution Reaction , 2017, Advanced materials.

[36]  Hao Zhang,et al.  ZnO template strategy for the synthesis of 3D interconnected graphene nanocapsules from coal tar pitch as supercapacitor electrode materials , 2017 .

[37]  L. Dai,et al.  Plasma-Engraved Co3 O4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction. , 2016, Angewandte Chemie.

[38]  Bin Zhang,et al.  Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction. , 2016, Chemical Society reviews.

[39]  Wei Chen,et al.  A Review of Phosphide‐Based Materials for Electrocatalytic Hydrogen Evolution , 2015 .

[40]  Zhengyan Lun,et al.  Non-precious alloy encapsulated in nitrogen-doped graphene layers derived from MOFs as an active and durable hydrogen evolution reaction catalyst , 2015 .

[41]  Min Gyu Kim,et al.  Metal (Ni, Co)‐Metal Oxides/Graphene Nanocomposites as Multifunctional Electrocatalysts , 2015 .

[42]  Xiaoxin Zou,et al.  Noble metal-free hydrogen evolution catalysts for water splitting. , 2015, Chemical Society reviews.

[43]  Yong Wang,et al.  In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution. , 2015, Journal of the American Chemical Society.

[44]  A. B. Fuertes,et al.  Hydrothermal carbonization of biomass as a route for the sequestration of CO2: chemical and structural properties of the carbonized products. , 2011 .

[45]  Xuezhi Duan,et al.  In situ transformation of 3D Co3O4 nanoparticles to 2D nanosheets with rich surface oxygen vacancies to boost hydrogen generation from NaBH4 , 2021 .

[46]  Weiyou Yang,et al.  ZIF-derived two-dimensional Co@Carbon hybrid: Toward highly efficient trifunctional electrocatalysts , 2021 .

[47]  Yaocai Bai,et al.  Porous cobalt oxide nanoplates enriched with oxygen vacancies for oxygen evolution reaction , 2018 .

[48]  L. Dai,et al.  Plasma-Engraved Co 3 O 4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction , 2016 .

[49]  Baoliang Chen,et al.  Aromatic and hydrophobic surfaces of wood-derived biochar enhance perchlorate adsorption via hydrogen bonding to oxygen-containing organic groups. , 2014, Environmental science & technology.