{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,7]],"date-time":"2026-05-07T13:21:43Z","timestamp":1778160103494,"version":"3.51.4"},"reference-count":48,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2026,5,6]],"date-time":"2026-05-06T00:00:00Z","timestamp":1778025600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100012166","name":"National Key Research and Development Program of China","doi-asserted-by":"publisher","award":["2021YFA1501802"],"award-info":[{"award-number":["2021YFA1501802"]}],"id":[{"id":"10.13039\/501100012166","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100011175","name":"State Key Laboratory of Heavy Oil Processing","doi-asserted-by":"publisher","award":["SKLHOP202403006"],"award-info":[{"award-number":["SKLHOP202403006"]}],"id":[{"id":"10.13039\/501100011175","id-type":"DOI","asserted-by":"publisher"}]},{"name":"State Key Laboratory of Catalysis in DICP","award":["N-19-08"],"award-info":[{"award-number":["N-19-08"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Nanomaterials"],"abstract":"<jats:p>The development of efficient catalysts for acetylene hydrochlorination is critical for replacing the industrially prevalent mercury chloride catalysts. Herein, a defective nitrogen-doped carbon material (NC-APT) is engineered via a facile co-polymerization of pyrrole, aniline, and thiophene, followed by a controlled calcination procedure. This co-polymerization strategy introduces abundant structural defects compared to mono-polymerization processes, primarily due to the lattice mismatch and steric hindrance between the distinct monomers, which disrupts the regularity of the polymer chain and prevents graphitic ordering. The resulting NC-APT catalyst features a high specific surface area of 375.7 m2\u00b7g\u22121 and a substantial nitrogen dopant content of 14.4%, with 81% of the nitrogen existing as catalytically active edge structures (pyrrolic and pyridinic N). Consequently, the catalyst delivers exceptional performance, achieving 92% acetylene conversion at 220 \u00b0C with a C2H2 gas hourly space velocity (GHSV) of 80 h\u22121. This performance significantly outperforms many reported metal-free counterparts and rivals that of traditional metal-based catalysts. This work offers new insights into the rational design of carbon-based, metal-free catalysts through monomer mismatch engineering.<\/jats:p>","DOI":"10.3390\/nano16090568","type":"journal-article","created":{"date-parts":[[2026,5,7]],"date-time":"2026-05-07T12:15:07Z","timestamp":1778156107000},"page":"568","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Engineering of Edge-Enriched Nitrogen-Doped Porous Carbon as a High-Performance Metal-Free Catalyst for Acetylene Hydrochlorination"],"prefix":"10.3390","volume":"16","author":[{"given":"Zhenzhen","family":"Zhang","sequence":"first","affiliation":[{"name":"Institute of Materials for Energy and Environment, College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dashuai","family":"Zhang","sequence":"additional","affiliation":[{"name":"Shandong Provincial Key Laboratory of Monocrystalline Silicon Semiconductor Materials and Technology, College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yalei","family":"Hao","sequence":"additional","affiliation":[{"name":"Institute of Materials for Energy and Environment, College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Guangzong","family":"Fang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7498-5752","authenticated-orcid":false,"given":"Xingyun","family":"Li","sequence":"additional","affiliation":[{"name":"Institute of Materials for Energy and Environment, College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2528-1155","authenticated-orcid":false,"given":"Jian","family":"Qi","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Biopharmaceutical Preparation and Delivery, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2026,5,6]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Liu, Y., Zhao, L., Zhang, Y., Zhang, L., and Zan, X. (2020). Progress and Challenges of Mercury-Free Catalysis for Acetylene Hydrochlorination. Catalysts, 10.","DOI":"10.3390\/catal10101218"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"215541","DOI":"10.1016\/j.ccr.2023.215541","article-title":"Progress of p-block element-regulated catalysts for acetylene hydrochlorination","volume":"500","author":"Wang","year":"2024","journal-title":"Coord. Chem. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"3838","DOI":"10.1039\/D4CY00549J","article-title":"Progress in mercury-free catalysts for acetylene hydrochlorination","volume":"14","author":"Qiao","year":"2024","journal-title":"Catal. Sci. Technol."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"20401","DOI":"10.1021\/acs.jpcc.2c06889","article-title":"Effect of Different Heteroatoms Anchoring a Cu Single-Atom Catalyst on Acetylene Hydrochlorination","volume":"126","author":"Jia","year":"2022","journal-title":"J. Phys. Chem. C"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"878","DOI":"10.1002\/slct.201904749","article-title":"Macroporous Carbon Material with High Nitrogen Content for Excellent Catalytic Performance of Acetylene Hydrochlorination","volume":"5","author":"Lu","year":"2020","journal-title":"ChemistrySelect"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"34612","DOI":"10.1039\/D0RA06256A","article-title":"Sulphur-doped activated carbon as a metal-free catalyst for acetylene hydrochlorination","volume":"10","author":"Qi","year":"2020","journal-title":"RSC Adv."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2007221","DOI":"10.1002\/smll.202007221","article-title":"Sulfur Promotion in Au\/C Catalyzed Acetylene Hydrochlorination","volume":"17","author":"Dawson","year":"2021","journal-title":"Small"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1683","DOI":"10.1016\/S1872-2067(20)63616-6","article-title":"Carbon-supported ruthenium catalysts prepared by a coordination strategy for acetylene hydrochlorination","volume":"41","author":"Wang","year":"2020","journal-title":"Chin. J. Catal."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"606","DOI":"10.1038\/s41565-022-01105-4","article-title":"Performance descriptors of nanostructured metal catalysts for acetylene hydrochlorination","volume":"17","author":"Kaiser","year":"2022","journal-title":"Nat. Nanotechnol."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"5657","DOI":"10.1039\/D4QI00756E","article-title":"A hierarchically porous carbon stabilized atomically dispersed Au catalyst for acetylene hydrochlorination","volume":"11","author":"Lan","year":"2024","journal-title":"Inorg. Chem. Front."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"17057","DOI":"10.1021\/acs.iecr.2c03009","article-title":"Construction of a Thermally Stable Low-HgCl2 Catalyst via Chalcogen Bonding and Its Enhanced Activity in Acetylene Hydrochlorination","volume":"61","author":"Sun","year":"2022","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"46992","DOI":"10.1021\/acsomega.2c06109","article-title":"Development of Low-Cost Porous Carbons Through Alkali Activation of Crop Waste for CO2 Capture","volume":"7","author":"Wang","year":"2022","journal-title":"ACS Omega"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"118","DOI":"10.1016\/j.cej.2019.04.008","article-title":"N-doped activated carbon from used dyeing wastewater adsorbent as a metal-free catalyst for acetylene hydrochlorination","volume":"371","author":"Mei","year":"2019","journal-title":"Chem. Eng. J."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"33069","DOI":"10.1039\/D2RA05979G","article-title":"The development of activated carbon from corncob for CO2 capture","volume":"12","author":"Wang","year":"2022","journal-title":"RSC Adv."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"4043","DOI":"10.1002\/anie.201912857","article-title":"Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts","volume":"59","author":"Koshy","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2300275","DOI":"10.1002\/smsc.202300275","article-title":"Design and 3D Printing of Polyacrylonitrile-Derived Nanostructured Carbon Architectures","volume":"4","author":"Bobrin","year":"2024","journal-title":"Small Sci."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"3688","DOI":"10.1038\/ncomms4688","article-title":"Silicon carbide-derived carbon nanocomposite as a substitute for mercury in the catalytic hydrochlorination of acetylene","volume":"5","author":"Li","year":"2014","journal-title":"Nat. Commun."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"6178","DOI":"10.1007\/s12274-022-5237-y","article-title":"Free radicals induced ultra-rapid synthesis of N-doped carbon sphere catalyst with boosted pyrrolic N active sites for efficient acetylene hydrochlorination","volume":"16","author":"Bao","year":"2022","journal-title":"Nano Res."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"e202425439","DOI":"10.1002\/anie.202425439","article-title":"g-C3N4 S-Scheme Homojunction through Van der Waals Interface Regulation by Intrinsic Polymerization Tailoring for Enhanced Photo","volume":"64","author":"Zhu","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2652","DOI":"10.1039\/D4PY00425F","article-title":"Novel nitrogen-rich conjugated microporous polymers for efficient capture of iodine and methyl iodide","volume":"15","author":"Yang","year":"2024","journal-title":"Polym. Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"39789","DOI":"10.1038\/srep39789","article-title":"Nitrogen-Doped Carbon Derived from ZIF-8 as a High-Performance Metal-Free Catalyst for Acetylene Hydrochlorination","volume":"7","author":"Chao","year":"2017","journal-title":"Sci. Rep."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"17979","DOI":"10.1021\/acssuschemeng.9b04767","article-title":"Constructing Pyridinic N-Rich Aromatic Ladder Structure Catalysts from Industrially Available Polyacrylonitrile Resin for Acetylene Hydrochlorination","volume":"7","author":"Qiao","year":"2019","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1114","DOI":"10.1021\/acscatal.7b03031","article-title":"Descriptors for High-Performance Nitrogen-Doped Carbon Catalysts in Acetylene Hydrochlorination","volume":"8","author":"Lin","year":"2018","journal-title":"ACS Catal."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"129451","DOI":"10.1016\/j.seppur.2024.129451","article-title":"A robust aerogel incorporated with phthalocyanine-based porous organic polymers for highly efficient gold extraction","volume":"354","author":"Chen","year":"2025","journal-title":"Sep. Purif. Technol."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"298","DOI":"10.1016\/j.jcis.2019.10.102","article-title":"MoS2\/Au0\/N-CNT derived from Au(III) extraction by polypyrrole\/MoS4 as an electrocatalyst for hydrogen evolution reaction","volume":"561","author":"Yang","year":"2020","journal-title":"J. Colloid Interface Sci."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"138702","DOI":"10.1016\/j.jcis.2025.138702","article-title":"Engineering ion-framed porous organic polymer for synergistic high-capacity adsorption and ultra-trace recovery of gold","volume":"701","author":"Ding","year":"2026","journal-title":"J. Colloid Interface Sci."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"e202200161","DOI":"10.1002\/celc.202200161","article-title":"Polypyrrole and Polythiophene Modified Carbon Nanotube-Based Cathode Catalysts for Anion Exchange Membrane Fuel Cell","volume":"9","author":"Sokka","year":"2022","journal-title":"ChemElectroChem"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"145472","DOI":"10.1016\/j.cej.2023.145472","article-title":"Highly porous polyaniline- or polypyrrole-derived carbons: Preparation, characterization, and applications in adsorption","volume":"474","author":"Khan","year":"2023","journal-title":"Chem. Eng. J."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"587","DOI":"10.1039\/D5SE01542A","article-title":"Engineering accessible Fe-N sites in polypyrrole-derived catalysts via a dynamic coordination strategy","volume":"10","author":"Li","year":"2026","journal-title":"Sustain. Energy Fuels"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"80","DOI":"10.1016\/j.jtice.2021.06.048","article-title":"Microporous nitrogen-doped carbon from polyaniline as a highly efficient and stable catalyst for acetylene hydrochlorination","volume":"126","author":"Tao","year":"2021","journal-title":"J. Taiwan Inst. Chem. Eng."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"234","DOI":"10.1016\/j.apcatb.2013.05.031","article-title":"AuCl3 on polypyrrole-modified carbon nanotubes as acetylene hydrochlorination catalysts","volume":"142\u2013143","author":"Li","year":"2013","journal-title":"Appl. Catal. B Environ."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"3471","DOI":"10.1007\/s11164-013-1463-y","article-title":"Synthesis, crystal structure, and antibacterial activity of magnesium(II) coordination polymers formed by hydrogen bonding","volume":"41","author":"Tai","year":"2013","journal-title":"Res. Chem. Intermed."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1016\/j.jes.2025.08.061","article-title":"Graphitic carbon nitride photocatalysts for sustainable energy and environmental remediation: Performance optimization and future perspectives","volume":"163","author":"Zhang","year":"2026","journal-title":"J. Environ. Sci."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"14221","DOI":"10.1002\/chem.202001722","article-title":"The Effect of \u03b1-Branched Side Chains on the Structural and Opto-Electronic Properties of Poly(Diketopyrrolopyrrole-alt-Terthiophene)","volume":"26","author":"Saes","year":"2020","journal-title":"Chem. A Eur. J."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"7655","DOI":"10.1021\/acs.jpca.7b07582","article-title":"Modeling Oil Shale Pyrolysis: High-Temperature Unimolecular Decomposition Pathways for Thiophene","volume":"121","author":"Vasiliou","year":"2017","journal-title":"J. Phys. Chem. A"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1462","DOI":"10.1016\/j.cclet.2019.10.002","article-title":"Research progress of graphene-based nanomaterials for the environmental remediation","volume":"31","author":"Pan","year":"2020","journal-title":"Chin. Chem. Lett."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"161","DOI":"10.1016\/j.jcat.2017.12.016","article-title":"Sulfur and nitrogen co-doped mesoporous carbon with enhanced performance for acetylene hydrochlorination","volume":"359","author":"Dong","year":"2018","journal-title":"J. Catal."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"20131","DOI":"10.1039\/C8NJ04410D","article-title":"Nitrogen doped nanoflower porous carbon as a nonmetal catalyst for acetylene hydrochlorination","volume":"42","author":"Liu","year":"2018","journal-title":"New J. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Shen, Z., Xing, P., Wen, K., and Jiang, B. (2023). Cationic Covalent Triazine Network: A Metal-Free Catalyst for Effective Acetylene Hydrochlorination. Catalysts, 13.","DOI":"10.3390\/catal13020432"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"467","DOI":"10.1016\/j.compositesb.2014.10.007","article-title":"Preparation and characterization of poly(3-octylthiophene)\/carbon fiber thermoelectric composite materials","volume":"69","author":"Wang","year":"2015","journal-title":"Compos. Part B Eng."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"47109","DOI":"10.1021\/jacs.5c13270","article-title":"Boron Nitride-Confined Nanographene as a Metal-Free Catalyst for Acetylene Hydrochlorination","volume":"147","author":"Guo","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"116","DOI":"10.1016\/j.apcatb.2017.03.046","article-title":"Deactivation mechanism and regeneration of carbon nanocomposite catalyst for acetylene hydrochlorination","volume":"210","author":"Li","year":"2017","journal-title":"Appl. Catal. B Environ."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"288","DOI":"10.1016\/j.jcat.2013.12.006","article-title":"A novel, non-metallic graphitic carbon nitride catalyst for acetylene hydrochlorination","volume":"311","author":"Li","year":"2014","journal-title":"J. Catal."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"7461","DOI":"10.1039\/C4RA13862G","article-title":"Nitrogen-doped active carbon as a metal-free catalyst for acetylene hydrochlorination","volume":"5","author":"Zhang","year":"2015","journal-title":"RSC Adv."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"484","DOI":"10.1016\/j.cjche.2015.11.028","article-title":"Oxygen and nitrogen-doped metal-free carbon catalysts for hydrochlorination of acetylene","volume":"24","author":"Zhang","year":"2016","journal-title":"Chin. J. Chem. Eng."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"68","DOI":"10.1016\/j.apcata.2017.09.025","article-title":"A novel S, N dual doped carbon catalyst for acetylene hydrochlorination","volume":"549","author":"Wang","year":"2018","journal-title":"Appl. Catal. A Gen."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"72","DOI":"10.1016\/j.apcata.2018.07.025","article-title":"Effect of carbon defects on the nitrogen-doped carbon catalytic performance for acetylene hydrochlorination","volume":"564","author":"Wang","year":"2018","journal-title":"Appl. Catal. A Gen."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"14556","DOI":"10.1039\/D0RA00475H","article-title":"Nitrogen-doped porous carbon from biomass with superior catalytic performance for acetylene hydrochlorination","volume":"10","author":"Shen","year":"2020","journal-title":"RSC Adv."}],"container-title":["Nanomaterials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-4991\/16\/9\/568\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,5,7]],"date-time":"2026-05-07T13:05:34Z","timestamp":1778159134000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-4991\/16\/9\/568"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,5,6]]},"references-count":48,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2026,5]]}},"alternative-id":["nano16090568"],"URL":"https:\/\/doi.org\/10.3390\/nano16090568","relation":{},"ISSN":["2079-4991"],"issn-type":[{"value":"2079-4991","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,5,6]]}}}