Recyclable Perovskite/g-C3N4 Heterojunction Enabling Photo-redox Nickel-Catalyzed C(sp2)-C(sp3) Cross-Electrophile Coupling

Recyclable Perovskite/g-C3N4 Heterojunction Enabling Photo-redox Nickel-Catalyzed C(sp2)-C(sp3) Cross-Electrophile Coupling | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Recyclable Perovskite/g-C 3 N 4 Heterojunction Enabling Photo-redox Nickel-Catalyzed C(sp 2 )-C(sp 3 ) Cross-Electrophile Coupling Renyi Shi, Rui Wang, Donghao Huo, Shentong Xie, Honghui Ou This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7904779/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Nickel-catalyzed cross-electrophile coupling (XEC) provides an efficient and cost-effective strategy for constructing C(sp 2 )-C(sp 3 ) bonds, a pivotal transformation for diversifying molecular architectures in pharmaceutical and agrochemical synthesis. However, conventional XEC methodologies usually require stoichiometric metal reductants, which pose safety risks, reaction instability, and environmental concerns. To circumvent these limitations, merging nickel catalysis with photoredox catalysis has emerged as a promising alternative. Central to this approach is to develop highly efficient, easy-to-prepare and recyclable photocatalysts, which can drive the reaction under mild conditions. In this work, we present a recyclable LaFeO 3 /LaCoO 3 /g-C 3 N 4 heterojunction. The stepped band structure and dual Z-scheme carrier migration paths significantly enhance photocatalytic performance by synergistically increasing redox potentials and extending the lifetime of photogenerated charge carriers through efficient interfacial charge transfer. Leveraging this heterojunction, we have developed a nickel/photoredox dual-catalyzed XEC between aryl iodides and alkyl halides, eliminating the need for stoichiometric metal reductants. This catalytic system demonstrates broad compatibility with diverse aryl iodides and alkyl halides, affording the desired products with up to 98% yields. The perovskite/g-C 3 N 4 photocatalyst enables quantitative catalyst recovery and maintains consistent activity over 5 cycles (> 90% yield), substantially improving process sustainability. Mechanistic studies reveal that photogenerated electrons from the heterojunction simultaneously mediate both alkyl halide activation and nickel catalyst reduction. Physical sciences/Chemistry/Chemical synthesis/Synthetic chemistry methodology Physical sciences/Chemistry/Catalysis Introduction Organic chemistry primarily revolves around the formation of carbon-carbon bonds. One of the most reliable methods for constructing C(sp 3 )–C(sp 2 ) bonds is the transition-metal-catalyzed cross-coupling reactions between electrophilic organohalides and nucleophilic organometallic reagents. [ 1 – 6 ] However, due to the inherent limitations associated with preformed carbon nucleophiles which are typically derived from the corresponding organohalides, cross-electrophile coupling (XEC) of electrophilic organohalides has emerged as a viable alternative for constructing C(sp 3 )-C(sp 2 ) bonds. [ 7 – 12 ] The most prevalent strategy for XEC involves the combination of nickel catalysis with metallic reducing agents, such as Mn or Zn powders (Fig. 1 a). [ 13 – 16 ] The use of metal powders poses several challenges: a) safety hazards stemming from the large excesses of flammable metal powders; b) the production of environmentally unfriendly metal waste (e.g., MnX 2 , ZnX 2 ) that is difficult to separate and is subject to stringent disposal regulations; c) reaction instability due to heterogeneity/mixing, inconsistent metallic reductant quality. In response to these concerns, photochemical alternatives for cross-electrophile coupling have been developed. [ 17 ] Significant advancements have been made by integrating nickel catalysis with photocatalysis to create activation modes of substrates and circumvent the need for metal powders (Fig. 1 b). [ 18 – 39 ] However, most of these nickel/photoredox dual-catalyzed cross-electrophile coupling reactions rely on precious metal photocatalysts, such as Ir, Ru or unrecyclable organic photocatalysts. Furthermore, homogeneous reaction conditions limit photocatalyst recyclability. There is consequently an urgent need to develop highly efficient, easily prepared, and recyclable photocatalysts to enable greener and more sustainable cross-electrophile coupling reactions. Graphitic carbon nitride (g-C 3 N 4 ), metal-free polymeric semiconductor, has attracted intense interest for artificial photosynthesis, optoelectronics and heterogeneous catalysis owing to its low cost, facile synthesis from molecular precursors and exceptional chemical robustness. Its high density of C/N surface defects and large specific surface area endow pronounced adsorption affinity toward organic substrates. [ 40 – 47 ] Nevertheless, the practical implementation of bare g-C 3 N 4 in photocatalytic redox processes is severely hampered by (i) massive aggregation that demands excess solvent to dissolve reactants and disperse the catalyst, (ii) ultrafast charge-carrier recombination, (iii) low electron mobility, (iv) poor crystallinity and (v) a narrow visible-light-harvesting window, all of which conspire to suppress quantum efficiency and limit the scope of heterogeneous reaction manifolds. Perovskite materials demonstrate significant potential for addressing these challenges, owing to their superior light-harvesting capacity, adjustable band structures, and exceptional charge separation/transport characteristics (Fig. 1 c). [ 48 – 55 ] Here we introduce a fully recyclable LaFeO 3 /LaCoO 3 /g-C 3 N 4 double Z-scheme heterojunction that rectifies these intrinsic shortcomings. The engineered step-like band alignment and dual Z-pathway enforce vectorial interfacial charge transfer, simultaneously elevating the reduction/oxidation potentials and prolonging the lifetime of photogenerated carriers, thereby delivering a dramatic boost in photocatalytic performance. Capitalizing on this architecture, we establish a nickel/photoredox dual-catalytic cross-electrophile coupling (XEC) between aryl iodides and alkyl halides that operates without stoichiometric metallic reductants. The protocol exhibits broad substrate scope (> 40 examples) and furnishes the desired C(sp 2 )–C(sp 3 ) products in isolated yields up to 98%, underscoring the transformative potential of perovskite-decorated carbon nitride heterostructures for sustainable visible-light-driven organic synthesis. (Fig. 1 d). Results and discussion g-C 3 N 4 was prepared via the pyrolysis of urea, whereas the LaFeO 3 /LaCoO 3 /g-C 3 N 4 (LCFOCN-2) heterojunction—exhibiting the highest catalytic activity—was fabricated through a sequential sol–gel, calcination, and solvothermal protocol. (Detailed synthetic procedures are provided in SI Section S5.) The transmission electron spectroscopy (TEM) and scanning electron microscopy (SEM) images show a lump-like morphology of Perovskite/g-C 3 N 4 . 2D sheet-like LCFOCN-2 scaffolds are visualized by TEM, wherein LaFeO 3 /LaCoO 3 (LCFO) nanodomains are periodically embedded (Fig. 2 a and Fig. S5). Anticipatedly, LaFeO 3 and LaCoO 3 existed as single granular on graphite-like carbon nitride. The microstructure of the material may enhance electron transfer from the bulk to the surface phase, optimize interfacial properties, and improve catalytic performance. Figure 2 b illustrates the crystal microstructure of LCFO species on g-C₃N₄, with measured facet spacings of 0.272 nm (LaCoO₃ (-110)) and 0.383 nm (LaFeO₃ (110)). This indicates that the fired LCFO bulk phase contains two crystalline phases. Figure S6a shows that the XRD pattern of LCFO-1 exhibits characteristic peaks corresponding to LaCoO₃ (JCPDS card no. 84–0848), but lacks characteristic reflections of LaFeO₃. The broader peaks observed in LCFO-1 compared to those in LaCoO₃ may be attributed to the incorporation of LaFeO₃. Figure S6b presents the XRD patterns of pure LaCoO₃, LaFeO₃, g-C₃N₄, LCFO, and LCFOCN-2, revealing characteristic peaks for LCFO and g-C₃N₄ in LCFOCN-2. Energy-dispersive X-ray spectroscopy (EDS) elemental mapping (Fig. 2 c) reveals a uniform distribution of C and N, with La, Co, Fe, and O predominantly concentrated in LCFO-1. FTIR spectra revealed that the characteristic peaks of LCFOCN-2 primarily originate from g-C₃N₄. While the presence of LCFO-1 species was confirmed by XRD and TEM, their characteristic peaks were difficult to discern due to weak IR activity. The Brunauer-Emmett-Teller (BET) analysis of LCFOCN-2 indicated a high specific surface area of 61 m²/g (Fig. S10). This elevated surface area enhances the likelihood of catalyst contact with reactants, thereby improving catalytic efficiency. X-ray photoelectron spectroscopy (XPS) confirms the interaction between LCFO-1 and graphite-like carbon nitride. In the C1s XPS spectrum (Figure S11a), peaks at 284.8 eV and 288.2 eV correspond to C-C and N = C-N species, respectively. The N1s XPS spectra (Figure S11b) show binding energies for C-N, C = N, N-(C) 3 , and N-H. Further analysis of other elements is shown in Figures. S11c and d. Comparison of the XPS C1s and N1s spectra of LCFOCN-2 with those of g-C₃N₄ (Figs. 2 d and 2 e), LCFOCN-2 C and N exhibit shifts to lower binding energy positions, suggesting electron transfer from LaCoO 3 to these elements post-light irradiation, a state of electron excess in g-C 3 N 4 due to the absence of reaction substrates and sacrificial agents during testing. The electron transfer between different crystalline phases indicates the successful loading of LCFO onto g-C 3 N 4 . To further evaluate the catalytic performance of these photocatalysts, we conducted nickel/photoredox dual-catalyzed cross-electrophile coupling reactions between p-methoxyiodobenzene and benzyl chloride (Table 1 ). The self-synthesized LCFOCN-1 to LCFOCN-5 catalysts exhibited varying efficiencies due to their different loading ratios (Entries 1–5). Notably, LCFOCN-2 achieved a 98% yield under optimized conditions, employing nickel chloride as the coupling catalyst, 1,10-phenanthroline as the ligand, DMSO as the solvent, and triethanolamine (TEOA) as the sacrificial agent (Entry 1). In contrast, using g-C 3 N 4 as the photocatalyst resulted in a significantly lower yield of 22% (Entry 6). Compared to the commercially available organic photocatalyst 4CzIPN, our catalyst LCFOCN-2 demonstrated approximately threefold higher activity (Entry 7). The LCFO series alone showed negligible reactivity, with almost no detectable product formation (Entry 8). This can likely be attributed to the limited specific surface area of pure perovskite catalysts and the rapid recombination of photogenerated electron-hole pairs. Control experiments confirmed that the reaction did not proceed in the absence of light, photocatalyst, nickel catalyst, or ligand (Entries 9–12). Additionally, triethanolamine (TEOA) was also essential, as it acted as a scavenger for the photogenerated holes (Entry 13). Recyclability is a pivotal parameter for evaluating the practical viability of semi-homogeneous photocatalysts. To this end, the durability of LCFOCN-2 was assessed through consecutive catalytic cycles under standardized conditions. As illustrated in Fig. 3 , LCFOCN-2 consistently achieved a catalytic coupling reaction yield exceeding 90% over five consecutive cycles. The robust and stable catalytic performance of LCFOCN-2 highlights its remarkable catalytic efficiency for the coupling reaction and exceptional reusability. The reaction scope was systematically evaluated using 4-iodoanisole ( 1a ) as the aryl coupling partner with various alkyl halides. Alkyl-substituted benzyl chlorides exhibited excellent reactivity, yielding the coupled products in 41–88% ( 3b - 3f ). However, sterically hindered substrates ( 3c , 3d ) showed slightly lower yields. Notably, halogenated benzyl chlorides (-F, -Cl, -Br) proved compatible, enabling subsequent functionalization ( 3g - 3j ). Strongly electron-withdrawing groups such as cyano ( 3k ), ester ( 3l ) and acyl ( 3m ) moieties were well tolerated, further demonstrating the system’s functional group versatility. Benzyl chlorides substituted with electron-donating groups like -OMe could run the reaction smoothly with 1a ( 3n and 3o ). The cross-electrophile coupling yield was 30% for a thioether-containing substrate that had a strong coordination with transition metal ( 3p ). Vinyl and phenyl groups were tolerated in our reaction, giving the 35% and 67% yields respectively ( 3q and 3r ). Substrates containing aromatic groups that exist widely in biologically active molecules such as naphthalene ( 3s ) thiophene ( 3t ) and pyridine ( 3u ) ran the reaction in moderate to high yields. The protocol was extended to nonactivated alkyl halides: primary alkyl bromides with diverse functionalities (phenyl 3v , 53%; halogen 3w , 64%; cyclopentyl 3x , 53%; ketone 3y , 46%) afforded moderate yields despite the challenge of stabilizing non-benzylic radicals. For the secondary alkyl bromide, 4-bromotetrahydro-2H-pyran could couple with aryl iodides selectively under standard reaction conditions ( 3z ). Alkyl iodides substituted with phenyl ( 3aa ), ester ( 3ab ), and vinyl ( 3ac ) also served as suitable substrates, affording the desired products. Secondary iodocyclohexane ( 3ad ) and 4-iodotetrahydro-2H-pyran( 3ae ) gave the desired products in moderate yields. Furthermore, we explored the scope of aryl iodides, and the results are presented in Scheme 2 . Electron-deficient aryl iodides bearing ester (4a and 4b), cyano (4c), and ketone (4d and 4e) functional groups underwent coupling reactions efficiently. This protocol also demonstrated its effectiveness for electron-rich substrates, such as those with phenyl (4f), trifluoromethoxy (4g), morpholine (4h), and t -Bu (4i) groups. Halogens such as -F and -Cl were well tolerated (4j and 4k), thereby providing the potential for subsequent coupling reactions. Delightfully, a substrate containing an unprotected hydroxyl group also reacted with good efficiency, yielding the desired product (4l). The substrates containing medicinally relevant heterocycles like naphthalene (4m), thiophene (4n), pyridine (4o), benzo[d][1,3]dioxole (4p), and thiazole (4q) produced the desired products in moderate yields. This success significantly expanded the applicability of the method for constructing valuable heteroaryl-alkyl linkages. To gain deeper insight into the photocatalytic mechanism of the LCFOCN-2 system, we performed Mott-Schottky analysis and solid-state UV-vis diffuse reflectance spectroscopy (UV-Vis DRS) to evaluate its band structure characteristics. As shown in Figures S8a-S8c, the flat-band potentials determined from Mott-Schottky plots were − 1.30 eV for g-C₃N₄, -1.15 eV for LaCoO₃, and − 1.40 eV for LaFeO₃. Considering that all three materials are n-type semiconductors, their conduction band (CB) potentials can be estimated to lie approximately 0.1 eV more negative than the flat-band values. Based on this, we deduced the relative positions of the CBs in the composite system. The corresponding bandgap energies in Figures S8d-S8f, derived from Tauc plots based on UV-Vis DRS measurements in Figures S8g-S8i, were calculated to be 2.82 eV for g-C₃N₄, 2.88 eV for LaCoO₃, and 2.04 eV for LaFeO₃. These electronic structure parameters collectively support the formation of a stepwise dual Z-scheme heterojunction, as illustrated in Fig. 4 a. This configuration facilitates directional charge migration and effective charge separation, thereby enhancing the redox capability of the composite catalyst under visible light irradiation. Notably, the introduction of a minimal amount of LCFO into the g-C₃N₄ matrix is sufficient to achieve a significant improvement in photocatalytic activity, highlighting the efficiency of the designed heterostructure. To further elucidate the photophysical characteristics, photoluminescence (PL) and Time-Resolved Fluorescence Spectroscopy (TRFS) as depicted in Figs. 4 b and 4 c. Under 320 nm excitation, PL emission was recorded using a 340 nm long-pass filter to eliminate scattered excitation light. In general, PL intensity correlates inversely with carrier lifetime at a given quantum yield—higher emission intensity often reflects rapid carrier recombination. The significantly quenched PL intensity of LCFOCN-2 thus reveals suppressed carrier recombination and prolonged carrier lifetimes. The LCFOCN-2 sample exhibits a markedly reduced carrier recombination rate, which can be attributed to its unique double-Z band alignment. This architecture promotes more efficient spatial separation of photogenerated electron-hole pairs. In Figs. 4 c, LCFOCN-2 exhibits a mono-exponential lifetime of 9.2 ns, 12% longer than pristine g-C₃N₄, evidencing fewer surface traps and rationalizing its superior photocatalytic evolution. In agreement with this, in Fig. 4 d, LCFOCN-2 exhibited the highest photocurrent density among all tested samples, indicative of its superior charge separation efficiency, enhanced interfacial charge transport, and excellent potential in photocatalytic applications. To gain a deeper understanding of the mechanism underlying this reductive cross - coupling reaction, a series of control experiments were conducted (as shown in Scheme 3 ). When a radical scavenger, such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), was introduced into our standard reaction, no desired product was observed (Eq. 1). Instead, the benzyl radical adduct, 1-(benzyloxy)-2,2,6,6-tetramethylpiperidine, was obtained in a 46% yield. The addition of 1,1-diphenylethylene to the reaction also led to the formation of prop-1-ene-1,1,3-triyltribenzene 6 , which was detected by high-resolution mass spectrometry (HRMS) (Eq. 2). These findings suggest that alkyl radicals might be involved in the coupling reactions. When benzyl chloride or (3-iodopropyl)benzene was reacted with TEMPO under standard reaction conditions in the absence of a nickel catalyst, the radical adducts 5 or 7 were formed, respectively (Eqs. 3 and 4). This indicates that the direct single-electron transfer (SET) between alkyl halides and the photocatalyst results in the generation of alkyl radicals. The reaction between (iodomethyl)cyclopropane and 1a yielded 12% of 3af with an opened cyclopropyl ring (Eq. 5). Additionally, the reaction of 6-iodohex-1-ene and 1a gave a 42% yield of 1-(cyclopentylmethyl)-4-methoxybenzene (Eq. 6). These results further support the notion that alkyl radicals are likely involved in the coupling reactions. Based on the results described above, a plausible mechanism is proposed as shown in Scheme 4 . For the LCFOCN-2 photocatalyst, irradiation with blue light promotes electron excitation from the valence band to the conduction band, generating electron-hole pairs. The photogenerated electrons reduce the Ni II catalyst precursor to a Ni 0 species ( A ). Subsequent oxidative addition of aryl halides to the Ni 0 species produces a Ni II species ( B ). Simultaneously, single-electron transfer from the excited photocatalyst surface to alkyl halides produces alkyl radicals, which are captured by B to generate a Ni III intermediate ( C ). The reductive elimination of C yields the desired product and a Ni I species ( D ), which is subsequently reduced to the Ni 0 species ( A ) by the photocatalyst, thereby completing the catalytic cycle. Conclusions In summary, we have successfully developed a three-component dual S-type heterojunction that demonstrates excellent photocatalytic performance. This heterojunction is prepared from cost-effective, readily available materials with low chalcogenide loading. Leveraging this heterojunction, we have developed a nickel/photoredox dual-catalyzed cross-electrophile coupling between alkyl halides and aryl iodides under mild reaction conditions. The methodology demonstrates broad substrate scope, high functional group tolerance, and good chemoselectivity. The perovskite/g-C 3 N 4 heterostructure enables quantitative catalyst recovery and maintains consistent activity over 5 cycles (> 90% yield), substantially improving process sustainability. Mechanistic studies reveal that photogenerated electrons from the heterojunction simultaneously mediate both alkyl halide activation and nickel catalyst reduction. Our work establishes a new paradigm for designing heterogeneous photocatalysts for cross-electrophile coupling reactions. Declarations Competing interests The authors declare no competing interests. Author contributions R.S. directed the project. R.S. and H.O. conceived the idea, designed the experiments and wrote the manuscript. R.W. and D.H. performed the synthetic experiments. All of the authors participated in the discussion and preparation of the manuscript. Acknowledgements This work is supported by the “Young Talent Support Plan” of Xi’an Jiaotong University and the Natural Science Founda-tion of Shaanxi Province (2023-JC-QN-0102). We acknowledge Prof. Dan Ren and Prof. Zhun Hu for their assistance with material characteriza-tion. We also extend our thanks to Prof. Fubin Jiang and Kexin Zhang for their contribution to synthesis of catalysts. Data availability The authors declare that the data supporting the findings of this study are available within the article and Supplementary Information files or from the corresponding author upon request. The experimental procedures and characterization of all new compounds are provided in the Supplementary Information. References Miyaura N, Suzuki A (1995) Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. Chem Rev 95:2457–2483 Netherton MR, Fu GC (2004) Nickel-Catalyzed Cross-Couplings of Unactivated Alkyl Halides and Pseudohalides with Organometallic Compounds. 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Angew Chem Int Ed 61:e202207975 Brinkmann KO, Wang P, Lang F, Li W, Guo X, Zimmermann F, Olthof S, Neher D, Hou Y, Stolterfoht M, Wang T, Djurisic AB, Riedl T (2024) Perovskite-organic tandem solar cells. Nat Rev Mater 9:202–217 Jiang Q, Zhu K (2024) Rapid advances enabling high-performance inverted perovskite solar cells. Nat Rev Mater 9:399–419 Kaur J, Peter SC (2025) Two-Dimensional Perovskites for Photocatalytic CO2 Reduction. Angew Chem Int Ed 64:e202418708 Table 1 Table 1 is available in the Supplementary Files section. Schemes Schemes 1 to 4 are available in the Supplementary Files section Additional Declarations There is NO Competing Interest. Supplementary Files SI.pdf SI Schemes.docx Table1.docx Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7904779","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":532618573,"identity":"e9a6b875-5907-4ebb-a473-2d3c53ed6d5c","order_by":0,"name":"Renyi 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07:14:28","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":30237,"visible":true,"origin":"","legend":"","description":"","filename":"Table1.docx","url":"https://assets-eu.researchsquare.com/files/rs-7904779/v1/ced4ee25381a755e87f77c27.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"\u003cp\u003eRecyclable Perovskite/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e Heterojunction Enabling Photo-redox Nickel-Catalyzed C(sp\u003csup\u003e2\u003c/sup\u003e)-C(sp\u003csup\u003e3\u003c/sup\u003e) Cross-Electrophile Coupling\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eOrganic chemistry primarily revolves around the formation of carbon-carbon bonds. One of the most reliable methods for constructing C(sp\u003csup\u003e3\u003c/sup\u003e)\u0026ndash;C(sp\u003csup\u003e2\u003c/sup\u003e) bonds is the transition-metal-catalyzed cross-coupling reactions between electrophilic organohalides and nucleophilic organometallic reagents.\u003csup\u003e[\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]\u003c/sup\u003e However, due to the inherent limitations associated with preformed carbon nucleophiles which are typically derived from the corresponding organohalides, cross-electrophile coupling (XEC) of electrophilic organohalides has emerged as a viable alternative for constructing C(sp\u003csup\u003e3\u003c/sup\u003e)-C(sp\u003csup\u003e2\u003c/sup\u003e) bonds.\u003csup\u003e[\u003cspan additionalcitationids=\"CR8 CR9 CR10 CR11\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]\u003c/sup\u003e The most prevalent strategy for XEC involves the combination of nickel catalysis with metallic reducing agents, such as Mn or Zn powders (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea).\u003csup\u003e[\u003cspan additionalcitationids=\"CR14 CR15\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]\u003c/sup\u003e The use of metal powders poses several challenges: a) safety hazards stemming from the large excesses of flammable metal powders; b) the production of environmentally unfriendly metal waste (e.g., MnX\u003csub\u003e2\u003c/sub\u003e, ZnX\u003csub\u003e2\u003c/sub\u003e) that is difficult to separate and is subject to stringent disposal regulations; c) reaction instability due to heterogeneity/mixing, inconsistent metallic reductant quality.\u003c/p\u003e\u003cp\u003eIn response to these concerns, photochemical alternatives for cross-electrophile coupling have been developed.\u003csup\u003e[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]\u003c/sup\u003e Significant advancements have been made by integrating nickel catalysis with photocatalysis to create activation modes of substrates and circumvent the need for metal powders (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb).\u003csup\u003e[\u003cspan additionalcitationids=\"CR19 CR20 CR21 CR22 CR23 CR24 CR25 CR26 CR27 CR28 CR29 CR30 CR31 CR32 CR33 CR34 CR35 CR36 CR37 CR38\" citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]\u003c/sup\u003e However, most of these nickel/photoredox dual-catalyzed cross-electrophile coupling reactions rely on precious metal photocatalysts, such as Ir, Ru or unrecyclable organic photocatalysts. Furthermore, homogeneous reaction conditions limit photocatalyst recyclability. There is consequently an urgent need to develop highly efficient, easily prepared, and recyclable photocatalysts to enable greener and more sustainable cross-electrophile coupling reactions.\u003c/p\u003e\u003cp\u003eGraphitic carbon nitride (g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e), metal-free polymeric semiconductor, has attracted intense interest for artificial photosynthesis, optoelectronics and heterogeneous catalysis owing to its low cost, facile synthesis from molecular precursors and exceptional chemical robustness. Its high density of C/N surface defects and large specific surface area endow pronounced adsorption affinity toward organic substrates.\u003csup\u003e[\u003cspan additionalcitationids=\"CR41 CR42 CR43 CR44 CR45 CR46\" citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e]\u003c/sup\u003e Nevertheless, the practical implementation of bare g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e in photocatalytic redox processes is severely hampered by (i) massive aggregation that demands excess solvent to dissolve reactants and disperse the catalyst, (ii) ultrafast charge-carrier recombination, (iii) low electron mobility, (iv) poor crystallinity and (v) a narrow visible-light-harvesting window, all of which conspire to suppress quantum efficiency and limit the scope of heterogeneous reaction manifolds. Perovskite materials demonstrate significant potential for addressing these challenges, owing to their superior light-harvesting capacity, adjustable band structures, and exceptional charge separation/transport characteristics (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec).\u003csup\u003e[\u003cspan additionalcitationids=\"CR49 CR50 CR51 CR52 CR53 CR54\" citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e]\u003c/sup\u003e\u003c/p\u003e\u003cp\u003eHere we introduce a fully recyclable LaFeO\u003csub\u003e3\u003c/sub\u003e/LaCoO\u003csub\u003e3\u003c/sub\u003e/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e double Z-scheme heterojunction that rectifies these intrinsic shortcomings. The engineered step-like band alignment and dual Z-pathway enforce vectorial interfacial charge transfer, simultaneously elevating the reduction/oxidation potentials and prolonging the lifetime of photogenerated carriers, thereby delivering a dramatic boost in photocatalytic performance. Capitalizing on this architecture, we establish a nickel/photoredox dual-catalytic cross-electrophile coupling (XEC) between aryl iodides and alkyl halides that operates without stoichiometric metallic reductants. The protocol exhibits broad substrate scope (\u0026gt;\u0026thinsp;40 examples) and furnishes the desired C(sp\u003csup\u003e2\u003c/sup\u003e)\u0026ndash;C(sp\u003csup\u003e3\u003c/sup\u003e) products in isolated yields up to 98%, underscoring the transformative potential of perovskite-decorated carbon nitride heterostructures for sustainable visible-light-driven organic synthesis. (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed).\u003c/p\u003e\u003cp\u003e\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003eg-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e was prepared via the pyrolysis of urea, whereas the LaFeO\u003csub\u003e3\u003c/sub\u003e/LaCoO\u003csub\u003e3\u003c/sub\u003e/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e (LCFOCN-2) heterojunction\u0026mdash;exhibiting the highest catalytic activity\u0026mdash;was fabricated through a sequential sol\u0026ndash;gel, calcination, and solvothermal protocol. (Detailed synthetic procedures are provided in SI Section S5.) The transmission electron spectroscopy (TEM) and scanning electron microscopy (SEM) images show a lump-like morphology of Perovskite/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e. 2D sheet-like LCFOCN-2 scaffolds are visualized by TEM, wherein LaFeO\u003csub\u003e3\u003c/sub\u003e/LaCoO\u003csub\u003e3\u003c/sub\u003e (LCFO) nanodomains are periodically embedded (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea and Fig. S5). Anticipatedly, LaFeO\u003csub\u003e3\u003c/sub\u003e and LaCoO\u003csub\u003e3\u003c/sub\u003e existed as single granular on graphite-like carbon nitride. The microstructure of the material may enhance electron transfer from the bulk to the surface phase, optimize interfacial properties, and improve catalytic performance. Figure \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb illustrates the crystal microstructure of LCFO species on g-C₃N₄, with measured facet spacings of 0.272 nm (LaCoO₃ (-110)) and 0.383 nm (LaFeO₃ (110)). This indicates that the fired LCFO bulk phase contains two crystalline phases. Figure S6a shows that the XRD pattern of LCFO-1 exhibits characteristic peaks corresponding to LaCoO₃ (JCPDS card no. 84\u0026ndash;0848), but lacks characteristic reflections of LaFeO₃. The broader peaks observed in LCFO-1 compared to those in LaCoO₃ may be attributed to the incorporation of LaFeO₃. Figure S6b presents the XRD patterns of pure LaCoO₃, LaFeO₃, g-C₃N₄, LCFO, and LCFOCN-2, revealing characteristic peaks for LCFO and g-C₃N₄ in LCFOCN-2. Energy-dispersive X-ray spectroscopy (EDS) elemental mapping (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec) reveals a uniform distribution of C and N, with La, Co, Fe, and O predominantly concentrated in LCFO-1. FTIR spectra revealed that the characteristic peaks of LCFOCN-2 primarily originate from g-C₃N₄. While the presence of LCFO-1 species was confirmed by XRD and TEM, their characteristic peaks were difficult to discern due to weak IR activity. The Brunauer-Emmett-Teller (BET) analysis of LCFOCN-2 indicated a high specific surface area of 61 m\u0026sup2;/g (Fig. S10). This elevated surface area enhances the likelihood of catalyst contact with reactants, thereby improving catalytic efficiency.\u003c/p\u003e\n\u003cp\u003eX-ray photoelectron spectroscopy (XPS) confirms the interaction between LCFO-1 and graphite-like carbon nitride. In the C1s XPS spectrum (Figure S11a), peaks at 284.8 eV and 288.2 eV correspond to C-C and N\u0026thinsp;=\u0026thinsp;C-N species, respectively. The N1s XPS spectra (Figure S11b) show binding energies for C-N, C\u0026thinsp;=\u0026thinsp;N, N-(C)\u003csub\u003e3\u003c/sub\u003e, and N-H. Further analysis of other elements is shown in Figures. S11c and d. Comparison of the XPS C1s and N1s spectra of LCFOCN-2 with those of g-C₃N₄ (Figs. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed and \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ee), LCFOCN-2 C and N exhibit shifts to lower binding energy positions, suggesting electron transfer from LaCoO\u003csub\u003e3\u003c/sub\u003e to these elements post-light irradiation, a state of electron excess in g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e due to the absence of reaction substrates and sacrificial agents during testing. The electron transfer between different crystalline phases indicates the successful loading of LCFO onto g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eTo further evaluate the catalytic performance of these photocatalysts, we conducted nickel/photoredox dual-catalyzed cross-electrophile coupling reactions between p-methoxyiodobenzene and benzyl chloride (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). The self-synthesized LCFOCN-1 to LCFOCN-5 catalysts exhibited varying efficiencies due to their different loading ratios (Entries 1\u0026ndash;5). Notably, LCFOCN-2 achieved a 98% yield under optimized conditions, employing nickel chloride as the coupling catalyst, 1,10-phenanthroline as the ligand, DMSO as the solvent, and triethanolamine (TEOA) as the sacrificial agent (Entry 1). In contrast, using g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e as the photocatalyst resulted in a significantly lower yield of 22% (Entry 6). Compared to the commercially available organic photocatalyst 4CzIPN, our catalyst LCFOCN-2 demonstrated approximately threefold higher activity (Entry 7). The LCFO series alone showed negligible reactivity, with almost no detectable product formation (Entry 8). This can likely be attributed to the limited specific surface area of pure perovskite catalysts and the rapid recombination of photogenerated electron-hole pairs. Control experiments confirmed that the reaction did not proceed in the absence of light, photocatalyst, nickel catalyst, or ligand (Entries 9\u0026ndash;12). Additionally, triethanolamine (TEOA) was also essential, as it acted as a scavenger for the photogenerated holes (Entry 13).\u003c/p\u003e\n\u003cp\u003eRecyclability is a pivotal parameter for evaluating the practical viability of semi-homogeneous photocatalysts. To this end, the durability of LCFOCN-2 was assessed through consecutive catalytic cycles under standardized conditions. As illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, LCFOCN-2 consistently achieved a catalytic coupling reaction yield exceeding 90% over five consecutive cycles. The robust and stable catalytic performance of LCFOCN-2 highlights its remarkable catalytic efficiency for the coupling reaction and exceptional reusability.\u003c/p\u003e\n\u003cp\u003eThe reaction scope was systematically evaluated using 4-iodoanisole (\u003cstrong\u003e1a\u003c/strong\u003e) as the aryl coupling partner with various alkyl halides. Alkyl-substituted benzyl chlorides exhibited excellent reactivity, yielding the coupled products in 41\u0026ndash;88% (\u003cstrong\u003e3b\u003c/strong\u003e-\u003cstrong\u003e3f\u003c/strong\u003e). However, sterically hindered substrates (\u003cstrong\u003e3c\u003c/strong\u003e, \u003cstrong\u003e3d\u003c/strong\u003e) showed slightly lower yields. Notably, halogenated benzyl chlorides (-F, -Cl, -Br) proved compatible, enabling subsequent functionalization (\u003cstrong\u003e3g\u003c/strong\u003e-\u003cstrong\u003e3j\u003c/strong\u003e). Strongly electron-withdrawing groups such as cyano (\u003cstrong\u003e3k\u003c/strong\u003e), ester (\u003cstrong\u003e3l\u003c/strong\u003e) and acyl (\u003cstrong\u003e3m\u003c/strong\u003e) moieties were well tolerated, further demonstrating the system\u0026rsquo;s functional group versatility. Benzyl chlorides substituted with electron-donating groups like -OMe could run the reaction smoothly with \u003cstrong\u003e1a\u003c/strong\u003e (\u003cstrong\u003e3n\u003c/strong\u003e and \u003cstrong\u003e3o\u003c/strong\u003e). The cross-electrophile coupling yield was 30% for a thioether-containing substrate that had a strong coordination with transition metal (\u003cstrong\u003e3p\u003c/strong\u003e). Vinyl and phenyl groups were tolerated in our reaction, giving the 35% and 67% yields respectively (\u003cstrong\u003e3q\u003c/strong\u003e and \u003cstrong\u003e3r\u003c/strong\u003e). Substrates containing aromatic groups that exist widely in biologically active molecules such as naphthalene (\u003cstrong\u003e3s\u003c/strong\u003e) thiophene (\u003cstrong\u003e3t\u003c/strong\u003e) and pyridine (\u003cstrong\u003e3u\u003c/strong\u003e) ran the reaction in moderate to high yields.\u003c/p\u003e\n\u003cp\u003eThe protocol was extended to nonactivated alkyl halides: primary alkyl bromides with diverse functionalities (phenyl \u003cstrong\u003e3v\u003c/strong\u003e, 53%; halogen \u003cstrong\u003e3w\u003c/strong\u003e, 64%; cyclopentyl \u003cstrong\u003e3x\u003c/strong\u003e, 53%; ketone \u003cstrong\u003e3y\u003c/strong\u003e, 46%) afforded moderate yields despite the challenge of stabilizing non-benzylic radicals. For the secondary alkyl bromide, 4-bromotetrahydro-2H-pyran could couple with aryl iodides selectively under standard reaction conditions (\u003cstrong\u003e3z\u003c/strong\u003e). Alkyl iodides substituted with phenyl (\u003cstrong\u003e3aa\u003c/strong\u003e), ester (\u003cstrong\u003e3ab\u003c/strong\u003e), and vinyl (\u003cstrong\u003e3ac\u003c/strong\u003e) also served as suitable substrates, affording the desired products. Secondary iodocyclohexane (\u003cstrong\u003e3ad\u003c/strong\u003e) and 4-iodotetrahydro-2H-pyran(\u003cstrong\u003e3ae\u003c/strong\u003e) gave the desired products in moderate yields.\u003c/p\u003e\n\u003cp\u003eFurthermore, we explored the scope of aryl iodides, and the results are presented in Scheme \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. Electron-deficient aryl iodides bearing ester (4a and 4b), cyano (4c), and ketone (4d and 4e) functional groups underwent coupling reactions efficiently. This protocol also demonstrated its effectiveness for electron-rich substrates, such as those with phenyl (4f), trifluoromethoxy (4g), morpholine (4h), and \u003cem\u003et\u003c/em\u003e-Bu (4i) groups. Halogens such as -F and -Cl were well tolerated (4j and 4k), thereby providing the potential for subsequent coupling reactions. Delightfully, a substrate containing an unprotected hydroxyl group also reacted with good efficiency, yielding the desired product (4l). The substrates containing medicinally relevant heterocycles like naphthalene (4m), thiophene (4n), pyridine (4o), benzo[d][1,3]dioxole (4p), and thiazole (4q) produced the desired products in moderate yields. This success significantly expanded the applicability of the method for constructing valuable heteroaryl-alkyl linkages.\u003c/p\u003e\n\u003cp\u003eTo gain deeper insight into the photocatalytic mechanism of the LCFOCN-2 system, we performed Mott-Schottky analysis and solid-state UV-vis diffuse reflectance spectroscopy (UV-Vis DRS) to evaluate its band structure characteristics. As shown in Figures S8a-S8c, the flat-band potentials determined from Mott-Schottky plots were \u0026minus;\u0026thinsp;1.30 eV for g-C₃N₄, -1.15 eV for LaCoO₃, and \u0026minus;\u0026thinsp;1.40 eV for LaFeO₃. Considering that all three materials are n-type semiconductors, their conduction band (CB) potentials can be estimated to lie approximately 0.1 eV more negative than the flat-band values. Based on this, we deduced the relative positions of the CBs in the composite system. The corresponding bandgap energies in Figures S8d-S8f, derived from Tauc plots based on UV-Vis DRS measurements in Figures S8g-S8i, were calculated to be 2.82 eV for g-C₃N₄, 2.88 eV for LaCoO₃, and 2.04 eV for LaFeO₃.\u003c/p\u003e\n\u003cp\u003eThese electronic structure parameters collectively support the formation of a stepwise dual Z-scheme heterojunction, as illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea. This configuration facilitates directional charge migration and effective charge separation, thereby enhancing the redox capability of the composite catalyst under visible light irradiation. Notably, the introduction of a minimal amount of LCFO into the g-C₃N₄ matrix is sufficient to achieve a significant improvement in photocatalytic activity, highlighting the efficiency of the designed heterostructure.\u003c/p\u003e\n\u003cp\u003eTo further elucidate the photophysical characteristics, photoluminescence (PL) and Time-Resolved Fluorescence Spectroscopy (TRFS) as depicted in Figs. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb and \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec. Under 320 nm excitation, PL emission was recorded using a 340 nm long-pass filter to eliminate scattered excitation light. In general, PL intensity correlates inversely with carrier lifetime at a given quantum yield\u0026mdash;higher emission intensity often reflects rapid carrier recombination. The significantly quenched PL intensity of LCFOCN-2 thus reveals suppressed carrier recombination and prolonged carrier lifetimes. The LCFOCN-2 sample exhibits a markedly reduced carrier recombination rate, which can be attributed to its unique double-Z band alignment. This architecture promotes more efficient spatial separation of photogenerated electron-hole pairs. In Figs. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec, LCFOCN-2 exhibits a mono-exponential lifetime of 9.2 ns, 12% longer than pristine g-C₃N₄, evidencing fewer surface traps and rationalizing its superior photocatalytic evolution. In agreement with this, in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed, LCFOCN-2 exhibited the highest photocurrent density among all tested samples, indicative of its superior charge separation efficiency, enhanced interfacial charge transport, and excellent potential in photocatalytic applications.\u003c/p\u003e\n\u003cp\u003eTo gain a deeper understanding of the mechanism underlying this reductive cross - coupling reaction, a series of control experiments were conducted (as shown in Scheme \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e). When a radical scavenger, such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), was introduced into our standard reaction, no desired product was observed (Eq. 1). Instead, the benzyl radical adduct, 1-(benzyloxy)-2,2,6,6-tetramethylpiperidine, was obtained in a 46% yield. The addition of 1,1-diphenylethylene to the reaction also led to the formation of prop-1-ene-1,1,3-triyltribenzene \u003cstrong\u003e6\u003c/strong\u003e, which was detected by high-resolution mass spectrometry (HRMS) (Eq. 2). These findings suggest that alkyl radicals might be involved in the coupling reactions. When benzyl chloride or (3-iodopropyl)benzene was reacted with TEMPO under standard reaction conditions in the absence of a nickel catalyst, the radical adducts \u003cstrong\u003e5\u003c/strong\u003e or \u003cstrong\u003e7\u003c/strong\u003e were formed, respectively (Eqs. 3 and 4). This indicates that the direct single-electron transfer (SET) between alkyl halides and the photocatalyst results in the generation of alkyl radicals. The reaction between (iodomethyl)cyclopropane and \u003cstrong\u003e1a\u003c/strong\u003e yielded 12% of \u003cstrong\u003e3af\u003c/strong\u003e with an opened cyclopropyl ring (Eq. 5). Additionally, the reaction of 6-iodohex-1-ene and \u003cstrong\u003e1a\u003c/strong\u003e gave a 42% yield of 1-(cyclopentylmethyl)-4-methoxybenzene (Eq. 6). These results further support the notion that alkyl radicals are likely involved in the coupling reactions.\u003c/p\u003e\n\u003cp\u003eBased on the results described above, a plausible mechanism is proposed as shown in Scheme \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e. For the LCFOCN-2 photocatalyst, irradiation with blue light promotes electron excitation from the valence band to the conduction band, generating electron-hole pairs. The photogenerated electrons reduce the Ni\u003csup\u003eII\u003c/sup\u003e catalyst precursor to a Ni\u003csup\u003e0\u003c/sup\u003e species (\u003cstrong\u003eA\u003c/strong\u003e). Subsequent oxidative addition of aryl halides to the Ni\u003csup\u003e0\u003c/sup\u003e species produces a Ni\u003csup\u003eII\u003c/sup\u003e species (\u003cstrong\u003eB\u003c/strong\u003e). Simultaneously, single-electron transfer from the excited photocatalyst surface to alkyl halides produces alkyl radicals, which are captured by \u003cstrong\u003eB\u003c/strong\u003e to generate a Ni\u003csup\u003eIII\u003c/sup\u003e intermediate (\u003cstrong\u003eC\u003c/strong\u003e). The reductive elimination of \u003cstrong\u003eC\u003c/strong\u003e yields the desired product and a Ni\u003csup\u003eI\u003c/sup\u003e species (\u003cstrong\u003eD\u003c/strong\u003e), which is subsequently reduced to the Ni\u003csup\u003e0\u003c/sup\u003e species (\u003cstrong\u003eA\u003c/strong\u003e) by the photocatalyst, thereby completing the catalytic cycle.\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eIn summary, we have successfully developed a three-component dual S-type heterojunction that demonstrates excellent photocatalytic performance. This heterojunction is prepared from cost-effective, readily available materials with low chalcogenide loading. Leveraging this heterojunction, we have developed a nickel/photoredox dual-catalyzed cross-electrophile coupling between alkyl halides and aryl iodides under mild reaction conditions. The methodology demonstrates broad substrate scope, high functional group tolerance, and good chemoselectivity. The perovskite/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e heterostructure enables quantitative catalyst recovery and maintains consistent activity over 5 cycles (\u0026gt;\u0026thinsp;90% yield), substantially improving process sustainability. Mechanistic studies reveal that photogenerated electrons from the heterojunction simultaneously mediate both alkyl halide activation and nickel catalyst reduction. Our work establishes a new paradigm for designing heterogeneous photocatalysts for cross-electrophile coupling reactions.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eCompeting interests\u003c/h2\u003e\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\u003ch2\u003eAuthor contributions\u003c/h2\u003e\u003cp\u003eR.S. directed the project. R.S. and H.O. conceived the idea, designed the experiments and wrote the manuscript. R.W. and D.H. performed the synthetic experiments. All of the authors participated in the discussion and preparation of the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e\u003cp\u003eThis work is supported by the \u0026ldquo;Young Talent Support Plan\u0026rdquo; of Xi\u0026rsquo;an Jiaotong University and the Natural Science Founda-tion of Shaanxi Province (2023-JC-QN-0102). We acknowledge Prof. Dan Ren and Prof. Zhun Hu for their assistance with material characteriza-tion. We also extend our thanks to Prof. Fubin Jiang and Kexin Zhang for their contribution to synthesis of catalysts.\u003c/p\u003e\n\u003ch3\u003eData availability\u003c/h3\u003e\n\u003cp\u003eThe authors declare that the data supporting the findings of this study are available within the article and Supplementary Information files or from the corresponding author upon request. The experimental procedures and characterization of all new compounds are provided in the Supplementary Information.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eMiyaura N, Suzuki A (1995) Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. Chem Rev 95:2457\u0026ndash;2483\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eNetherton MR, Fu GC (2004) Nickel-Catalyzed Cross-Couplings of Unactivated Alkyl Halides and Pseudohalides with Organometallic Compounds. 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Angew Chem Int Ed 64:e202418708\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Table 1","content":"\u003cp\u003eTable 1 is available in the Supplementary Files section.\u003c/p\u003e"},{"header":"Schemes","content":"\u003cp\u003eSchemes 1 to 4 are available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7904779/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7904779/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eNickel-catalyzed cross-electrophile coupling (XEC) provides an efficient and cost-effective strategy for constructing C(sp\u003csup\u003e2\u003c/sup\u003e)-C(sp\u003csup\u003e3\u003c/sup\u003e) bonds, a pivotal transformation for diversifying molecular architectures in pharmaceutical and agrochemical synthesis. However, conventional XEC methodologies usually require stoichiometric metal reductants, which pose safety risks, reaction instability, and environmental concerns. To circumvent these limitations, merging nickel catalysis with photoredox catalysis has emerged as a promising alternative. Central to this approach is to develop highly efficient, easy-to-prepare and recyclable photocatalysts, which can drive the reaction under mild conditions. In this work, we present a recyclable LaFeO\u003csub\u003e3\u003c/sub\u003e/LaCoO\u003csub\u003e3\u003c/sub\u003e/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e heterojunction. The stepped band structure and dual Z-scheme carrier migration paths significantly enhance photocatalytic performance by synergistically increasing redox potentials and extending the lifetime of photogenerated charge carriers through efficient interfacial charge transfer. Leveraging this heterojunction, we have developed a nickel/photoredox dual-catalyzed XEC between aryl iodides and alkyl halides, eliminating the need for stoichiometric metal reductants. This catalytic system demonstrates broad compatibility with diverse aryl iodides and alkyl halides, affording the desired products with up to 98% yields. The perovskite/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e photocatalyst enables quantitative catalyst recovery and maintains consistent activity over 5 cycles (\u0026gt;\u0026thinsp;90% yield), substantially improving process sustainability. Mechanistic studies reveal that photogenerated electrons from the heterojunction simultaneously mediate both alkyl halide activation and nickel catalyst reduction.\u003c/p\u003e","manuscriptTitle":"Recyclable Perovskite/g-C3N4 Heterojunction Enabling Photo-redox Nickel-Catalyzed C(sp2)-C(sp3) Cross-Electrophile Coupling","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-29 07:14:24","doi":"10.21203/rs.3.rs-7904779/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"169535c8-bd1f-490f-9d3c-f6d6bd83ee18","owner":[],"postedDate":"October 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":57067481,"name":"Physical sciences/Chemistry/Chemical synthesis/Synthetic chemistry methodology"},{"id":57067482,"name":"Physical sciences/Chemistry/Catalysis"}],"tags":[],"updatedAt":"2026-04-15T14:02:29+00:00","versionOfRecord":[],"versionCreatedAt":"2025-10-29 07:14:24","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7904779","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7904779","identity":"rs-7904779","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}