Chinese Journal of Catalysis ›› 2026, Vol. 82: 1-41.DOI: 10.1016/S1872-2067(25)64927-8
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Syeda Maria Hashmib, Yilin Wangb, Nida Rehmanb, Xinyi Tanc,*(
), Javier García-Martínezd, Ume Aimane, Muhammad Sajidb, Zhenyu Suna,b,*(
)
Received:2025-06-26
Accepted:2025-10-27
Online:2026-03-18
Published:2026-03-05
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* E-mail: About author:Xinyi Tan (School of Materials Science and Engineering, Beijing Institute of Technology) received her B.S. degree from Jilin University (China) in 2017, and Ph.D. degree from University of California, Los Angeles (UCLA) in 2021. Since 2022, she has been working in Beijing Key Laboratory of Environmental Science and Engineering of Beijing Institute of Technology. Her research focus on new materials in electrocatalysis, energy storage and biomass with design of nanostructure of new catalysts and electrodes. She also works on technologies and industrialization for the efficient and green production of high-end chemical materials for chips from biomass. Her recent research mainly includes CO2 electroreduction, bio-electroreduction of CO2, high-capacity electrodes for lithium-ion/sodium-ion batteries and biomass conversion. She is Excellent Young Scientists (Overseas) of National Natural Science Foundation of China (2023).Supported by:Syeda Maria Hashmi, Yilin Wang, Nida Rehman, Xinyi Tan, Javier García-Martínez, Ume Aiman, Muhammad Sajid, Zhenyu Sun. Towards sustainable chemistry: Advances, challenges and opportunities in organic electrosynthesis[J]. Chinese Journal of Catalysis, 2026, 82: 1-41.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64927-8
Fig. 1. (a) Most common paths for electro-organic chemicals. Reproduced with permission from Ref. [27]. Copyright 2021, John Wiley and Sons. (b) Hydrogen peroxide is produced by electro-reducing oxygen. Reproduced with permission from Ref. [27]. Copyright 2021, John Wiley and Sons. (c) p-Anisaldehyde's industrial electrosynthesis from p-methoxytoluene. Reproduced with permission from Ref. [7]. Copyright 2020, Royal Society of Chemistry. (d) Methods for electrochemical methoxymethylation that have recently been published. Reproduced with permission from Ref. [7]. Copyright 2020, Royal Society of Chemistry. (e) An overview of electrochemical decarboxylation and the compounds that result under Hofer-Moest (multiple electron transfer) and Kolbe (single electron transfer) circumstances. Reproduced with permission from Ref. [7]. Copyright 2020, Royal Society of Chemistry. (f) Chemoselective deprotection of an alcohol under electrochemical conditions. Conditions: C(gr)/C(gr), NBu4BF4/NMP-iPrOH (93:7). Reproduced with permission from Ref. [7]. Copyright 2020, Royal Society of Chemistry. (g) Electrochemical hydrogenation of acetophenone. Reproduced with permission from Ref. [26]. Copyright 2013, Elsevier.
Fig. 2. (a) Indirect electrochemical synthesis of benzaldehyde from benzyl alcohol using TEMPO as a mediator. Reproduced with permission from Ref. [7]. Copyright 2020, Royal Society of Chemistry. (b) Photoelectrochemical TEMPO-mediated HMF oxidation. Reproduced with permission from Ref. [31]. Copyright 2015, Springer Nature. (c) TEMPO-mediated photooxidation of HMF at 1.04 V (vs. RHE) in a 0.5 mol L?1 borate buffer solution containing 5 mmol L?1 HMF. Reproduced with permission from Ref. [31]. Copyright 2015, Springer Nature.
Fig. 3. (a,b) Paired electrolysis and their types. Reproduced with permission from Refs. [36]. Copyright 2021, American Chemical Society. (c) Schematic illustration of RR-enabled ModES for the paired oxidation of 4-t-butyltoluene in methanol and reduction of oxygen to H2O2 in water compared with conventional electrolysis processes. Reproduced with permission from Ref. [34]. Copyright 2022, American Chemical Society.
Fig. 4. (a) Diagrammatic electrolysis within an undivided cell. Reproduced with permission from Ref. [39]. Copyright 2020, Wiley-VCH. (b) Graphics of electrolysis in a divided cell. Reproduced with permission from Ref. [39]. Copyright 2020, from Wiley-VCH. (c) Diagrammatic representation of working principle of a quasi-divided cell design. Reproduced with permission from Ref. [39]. Copyright 2020, Wiley-VCH. (d) BDD electrodes diagram. Reproduced with permission from Ref. [57]. Copyright 2022, American Chemical Society. (e) Top view of uncoated RVC samples' 3D-rendered CT scans, displaying different ppi grades. Reproduced with permission from Ref. [58]. Copyright 2018, Elsevier.
| Material | Advantage | Disadvantage | Ref. |
|---|---|---|---|
| Mercury (cathode) | renewable surface, allowing operation at extremely negative potentials without unwanted side reactions | rarely used, extremely poisonous (may produce organomercurial chemicals) | [ |
| Lead (cathode) | suitable for strong organic reductions | organic substances can simply passivate it (cleaning is required during the electrolysis process). | [ |
| Silver (plated) (cathode) | excellent for the reduction of organic halides | high cost | [ |
| Nickel (anode) | forming the strongly oxidizing agent NiOOH in basic conditions | high cost | [ |
| Zinc, iron, magnesium, and aluminium, (sacrificial anodes) | removing the need for a divided cell, producing Lewis acids in situ, and requiring a significant surplus of supporting electrolyte | electrode can corrode during electrolysis | [ |
| Carbon (cathode and anode) | high versatility, low cost, many different types (pyrolytic carbon, glassy carbon, graphite, etc.), large H2 evolution overpotential (as a cathode enables strong reductions), and ease of chemical modification | can be fragile, hard to clean | [ |
| Platinum (cathode and anode) | easy to clean, highly adaptable, high stability | enabling quick evolution of hydrogen, a poor choice for strong reductions, high cost | [ |
Table 1 Benefits and drawbacks of various electrode compositions.
| Material | Advantage | Disadvantage | Ref. |
|---|---|---|---|
| Mercury (cathode) | renewable surface, allowing operation at extremely negative potentials without unwanted side reactions | rarely used, extremely poisonous (may produce organomercurial chemicals) | [ |
| Lead (cathode) | suitable for strong organic reductions | organic substances can simply passivate it (cleaning is required during the electrolysis process). | [ |
| Silver (plated) (cathode) | excellent for the reduction of organic halides | high cost | [ |
| Nickel (anode) | forming the strongly oxidizing agent NiOOH in basic conditions | high cost | [ |
| Zinc, iron, magnesium, and aluminium, (sacrificial anodes) | removing the need for a divided cell, producing Lewis acids in situ, and requiring a significant surplus of supporting electrolyte | electrode can corrode during electrolysis | [ |
| Carbon (cathode and anode) | high versatility, low cost, many different types (pyrolytic carbon, glassy carbon, graphite, etc.), large H2 evolution overpotential (as a cathode enables strong reductions), and ease of chemical modification | can be fragile, hard to clean | [ |
| Platinum (cathode and anode) | easy to clean, highly adaptable, high stability | enabling quick evolution of hydrogen, a poor choice for strong reductions, high cost | [ |
Fig. 5. (a) Modified electrode W2C/N3.0C for alkoxylation of benzylic C-H bonds. Reproduced with permission from Ref. [120]. Copyright 2023, Elsevier. (b) Representation of pyrene-TEMPO immobilized on the surface of carbon nanotubes. Reproduced with permission from Ref. [120]. Copyright 2023, Elsevier. (c) Proposed mechanism for CNT/MOL-TEMPO modified electrode. Reproduced with permission from Ref. [120]. Copyright 2023, Elsevier. (d) Representation of CNT/MOL-TEMPO-CO2 and CNT/MOL-TEMPO-OPO3H2. Reproduced with permission from Ref. [121]. Copyright 2018, American Chemical Society. (e) A modified RuO2-SnO2-TiO2 electrode designed for the selective electrocatalytic CAL hydrogenation. Reproduced with permission from Ref. [112]. Copyright 2019, American Chemical Society. (f) The deposition of nanoparticles on a carbon support, their activation as an electrochemical synthesis catalyst, and the distribution of reaction products after a 12-hour reaction. Reproduced with permission from Ref. [119]. Copyright 2020, John Wiley and Sons.
Fig. 6. (a) Regioselective halogenation of arenes through dual Pd catalysis and electrochemical oxidation. Reproduced with permission from Ref. [141]. Copyright 2018, Royal Society of Chemistry. (b) CO2 and H2O electrocatalytically react to generate C-H bonds. Reproduced with permission from Ref. [151]. Copyright 2024, OAE Publishing Inc. (c) The proposed reaction mechanism for the electrocatalyzed reduction of CO2 on nickel phosphides. Reproduced with permission from Ref. [152]. Copyright 2018, RSC Publishing. (d) FE for CO2RR as a function of potential and catalyst composition. Reproduced with permission from Ref. [152]. Copyright 2018, RSC Publishing.
Fig. 8. (a) Enantioselective nickel-catalyzed electrochemical cross-coupling. Reproduced with permission from Ref. [93]. Copyright 2025, American Chemical Society. (b) Ni-catalyzed C(sp2)?C(sp3) cross-electrophile coupling. Reproduced with permission from Ref. [158]. Copyright 2024, John Wiley and Sons. (c) Ni-catalyzed Nozaki-Hiyama-Kishi coupling. Reproduced with permission from Ref. [159]. Copyright 2021, American Chemical Society. (d) Synthesis of acetic acid by reaction of methanol with CO2 and H2. Reproduced with permission from Ref. [162]. Copyright 2016, Springer.
Fig. 9. (a) Electrochemical aziridination of olefins. Reproduced with permission from Ref. [141]. Copyright 2018, Royal Society of Chemistry. (b) Synthesis of (aza) indoles using ferrocene as mediator. Reproduced with permission from Ref. [141]. Copyright 2018, Royal Society of Chemistry. (c) Synthesis of 1,4-benzoxazin-3-ones via anodic C-H amination. Reproduced with permission from Ref. [141]. Copyright 2018, Royal Society of Chemistry. (d) Electrocatalytic processes involving C-N interaction. (I) CO2 and NH3/N2 simultaneously reduced to formamide/acetamide/urea. (II) CO2 and NO3-/NO2- simultaneously. Reproduced with permission from Ref. [151]. Copyright 2024, OAE Publishing Inc.
Fig. 10. (a) Electrocatalytic processes involving C-O interaction. (I) Dimethyl carbonate produced electrochemically from CO2 without changing the redox state. (II) Cyclic carbonates produced electrochemically from CO2 and diols. (III) Cyclic carbonates produced electrochemically by CO2 and epoxides. Reproduced with permission from Ref. [151]. Copyright 2024, OAE Publishing Inc. (b) Schematic (above) of the suggested reaction mechanism for the synthesis of dimethyl carbonate from CO2 and a redox-neutral electrochemical apparatus for this process. An electrochemical synthetic pathway (below) for the synthesis of propylene carbonate from CO2 and propylene oxide. Reproduced with permission from Ref. [151]. Copyright 2024, OAE Publishing Inc.
Fig. 11. (a) Difunctionalization of alkenes by electrochemical formation of both C-S and C-O/N bonds. Reproduced with permission from Ref. [202]. Copyright 2024, Georg Thieme Verlag KG. (b) Difunctionalization of isocyanides. Reproduced with permission from Ref. [202]. Copyright 2024, Georg Thieme Verlag KG. (c) Direct anodic cross-dehydrogenative coupling of (hetero) arenes and thiophenols. Reproduced with permission from Ref. [141]. Copyright 2018, Royal Society of Chemistry.
Fig. 12. C-S coupling processes and their electrocatalytic byproducts. Reproduced with permission from Ref. [151]. Copyright 2024, OAE Publishing Inc.
| Bond type | Example | Advantage | Challenge | Ref. |
|---|---|---|---|---|
| C-H activation & functionalization | Pd-catalyzed C-H iodination followed by Suzuki coupling Pd-mediated electrooxidative homocoupling of alkynes Sanford group’s Pd-catalyzed electroacetoxylation Co-catalyzed C-H amination/oxygenation/annulation Ni-catalyzed C-H amination & alkoxylation Fe-catalyzed C-H arylation with DCIB or direct electro-oxidation | atom-efficient, avoiding prefunctionalization, enabling site-selective functionalization | selectivity control (stereo/regio), competing side reactions, mechanistic complexity | [ [ [ [ [ |
| C-C bond formation | Kolbe electrolysis cascade (Schäfer) electro-Ni catalyzed enantioselective reductive cross-coupling electrochemical oxidative cross-dehydrogenative coupling (CDC) electrochemical carbazole synthesis Cross-electrophile couplings with arylsulfonium salts (procter, Ritter, Yorimitsu) electroreductive Nozaki-Hiyama-Kishi (Ni-catalyzed) enantioselective electroreductive benzyl/alkenyl coupling electro-carboxylation of pyridines with CO2 | high atom economy, avoiding stoichiometric oxidants, sustainable & scalable | requiring careful catalyst design, product purification, selectivity limits | [ [ [ [ [ [ [ |
| C-N bond formation | electro-aziridination, mediator-based radical cyclization to indoles/imidazo-heterocycles (Xu) BDD-anode mediated diamination (Waldvogel) anodic C-H amination to benzoxazinones Electrochemical amination with N-tosyl sulfilimine CO2/N2 or CO2/NO3-/NO2- co-reduction to urea, amides, amines | direct, green routes to urea, amines, amides; reduing reliance on Haber-Bosch | mechanistic complexity, limited selectivity, need for dual-site catalysts | [ [ |
| C-O bond formation | electrochemical aryl-O coupling (Pd, Ni, Cu catalysis) Aryl-alkyl ether synthesis, electro-driven carbonyl, ether, ester formation | higher yields, simpler work-up, sustainability | competing β-hydride elimination, limited substrate scope | [ [ |
| C-S bond formation | electrochemical difunctionalization of alkenes (oxysulfenylation, aminosulfenylation) | expanding scope of sulfur-functionalized compounds | still less developed than C-N or C-O routes | [ |
| CO2 reduction (C-H bond formation) | Ni2P and related phosphides for selective multi-carbon CO2RR | producing C1-C4 products, high FE, low overpotential | requiring precise catalyst design, scale-up challenges | [ |
Table 2 Summary of different organic electrosynthetic reactions.
| Bond type | Example | Advantage | Challenge | Ref. |
|---|---|---|---|---|
| C-H activation & functionalization | Pd-catalyzed C-H iodination followed by Suzuki coupling Pd-mediated electrooxidative homocoupling of alkynes Sanford group’s Pd-catalyzed electroacetoxylation Co-catalyzed C-H amination/oxygenation/annulation Ni-catalyzed C-H amination & alkoxylation Fe-catalyzed C-H arylation with DCIB or direct electro-oxidation | atom-efficient, avoiding prefunctionalization, enabling site-selective functionalization | selectivity control (stereo/regio), competing side reactions, mechanistic complexity | [ [ [ [ [ |
| C-C bond formation | Kolbe electrolysis cascade (Schäfer) electro-Ni catalyzed enantioselective reductive cross-coupling electrochemical oxidative cross-dehydrogenative coupling (CDC) electrochemical carbazole synthesis Cross-electrophile couplings with arylsulfonium salts (procter, Ritter, Yorimitsu) electroreductive Nozaki-Hiyama-Kishi (Ni-catalyzed) enantioselective electroreductive benzyl/alkenyl coupling electro-carboxylation of pyridines with CO2 | high atom economy, avoiding stoichiometric oxidants, sustainable & scalable | requiring careful catalyst design, product purification, selectivity limits | [ [ [ [ [ [ [ |
| C-N bond formation | electro-aziridination, mediator-based radical cyclization to indoles/imidazo-heterocycles (Xu) BDD-anode mediated diamination (Waldvogel) anodic C-H amination to benzoxazinones Electrochemical amination with N-tosyl sulfilimine CO2/N2 or CO2/NO3-/NO2- co-reduction to urea, amides, amines | direct, green routes to urea, amines, amides; reduing reliance on Haber-Bosch | mechanistic complexity, limited selectivity, need for dual-site catalysts | [ [ |
| C-O bond formation | electrochemical aryl-O coupling (Pd, Ni, Cu catalysis) Aryl-alkyl ether synthesis, electro-driven carbonyl, ether, ester formation | higher yields, simpler work-up, sustainability | competing β-hydride elimination, limited substrate scope | [ [ |
| C-S bond formation | electrochemical difunctionalization of alkenes (oxysulfenylation, aminosulfenylation) | expanding scope of sulfur-functionalized compounds | still less developed than C-N or C-O routes | [ |
| CO2 reduction (C-H bond formation) | Ni2P and related phosphides for selective multi-carbon CO2RR | producing C1-C4 products, high FE, low overpotential | requiring precise catalyst design, scale-up challenges | [ |
| Bond type | Electrocatalyst | Reaction/Transformation | Advantage | Limitation | Ref. |
|---|---|---|---|---|---|
| C-H activation | Pd + electrooxidation | C-H iodination → Suzuki coupling | high site-selectivity, dual role (activation + coupling) | expensive, requiring halide source, risk of overoxidation | [ [ |
| Pd catalyst | electrochemical acetoxylation (C(sp²)-H, C(sp³)-H) | direct acetoxylation under mild electrochemical conditions | costly ligands, overoxidation risk | [ | |
| Co | C-H amination, oxygenation, annulation | earth-abundant, low-cost, enabling multiple C-H transformations | requiring high potentials, catalyst stability issues | [ | |
| Ni | C-H amination and alkoxylation | low-cost, sustainable, proof-of-concept for amides and alcohols | early-stage, limited substrate scope so far | [ | |
| Fe | C-H arylation | greener alternative, superior efficiency vs. DCIB oxidation | sensitive to electrode effects, optimization needed | [ | |
| CO2 reduction (C-H generation) | Ni2P & related phosphides | CO2 reduction → C-H bond formation (C1-C4 products) | producing multi-carbon products (C1-C4) at near-thermoneutral potential; high faradaic efficiency | requiring precise catalyst design, scale-up challenges | [ |
| C-C bond | Ni catalyst + electroreduction | Reductive cross-coupling (aziridines + alkenyl bromides) | enantioselective, inexpensive metal | chiral ligands required, substrate-dependent | [ |
| Ni catalyst | Nozaki-Hiyama-Kishi coupling | first enantioselective electroreductive variant | halide-sensitive, ligand dependence | [ | |
| Fe, Ni, Ru, Rh catalysts | C1 → C2+ (from CO2/CH4/MeOH) | broadening carbonylation pathways | high energy input, low selectivity | [ | |
| C-N bond | Cu NPs | CO + NH3 → acetamide | inexpensive NP catalyst, decent selectivity | NP aggregation, instability | [ |
| Cu catalyst | CO2 + NH3 → formamide | high FE, stabilizing intermediates | poor stability, limited scale | [ | |
| Cu catalysts | CO2 + NO3-/NO2- → amines | access to multiple amines via intermediate pairing | low yield, multi-step intermediates | [ | |
| C-O bond | Pd (BrettPhos, RockPhos, etc.) | Aryl ether synthesis | ligand control enables selectivity and efficiency | costly ligands, sensitive to air/moisture | [ |
| Ni catalysts | C-O ether coupling | cheap Pd alternative, functional group tolerance | lower activity, catalyst deactivation | [ | |
| Cu catalysts + neutral ligands | Aryl-alkyl ethers | reducing alcohol excess, pharma relevance | ligand-dependent, recyclability issues | [ | |
| Mn(II) catalysts | Indole dearomatization with alcohols/NHTosylates (via Langlois’ reagent) | enabling electrochemical C-O cyclization; access to indolines | requiring specific nucleophiles; substrate limitations | [ |
Table 3 Summary of the state-of-the-art electrocatalysts for C?H, C?C, C?N, and C?O.
| Bond type | Electrocatalyst | Reaction/Transformation | Advantage | Limitation | Ref. |
|---|---|---|---|---|---|
| C-H activation | Pd + electrooxidation | C-H iodination → Suzuki coupling | high site-selectivity, dual role (activation + coupling) | expensive, requiring halide source, risk of overoxidation | [ [ |
| Pd catalyst | electrochemical acetoxylation (C(sp²)-H, C(sp³)-H) | direct acetoxylation under mild electrochemical conditions | costly ligands, overoxidation risk | [ | |
| Co | C-H amination, oxygenation, annulation | earth-abundant, low-cost, enabling multiple C-H transformations | requiring high potentials, catalyst stability issues | [ | |
| Ni | C-H amination and alkoxylation | low-cost, sustainable, proof-of-concept for amides and alcohols | early-stage, limited substrate scope so far | [ | |
| Fe | C-H arylation | greener alternative, superior efficiency vs. DCIB oxidation | sensitive to electrode effects, optimization needed | [ | |
| CO2 reduction (C-H generation) | Ni2P & related phosphides | CO2 reduction → C-H bond formation (C1-C4 products) | producing multi-carbon products (C1-C4) at near-thermoneutral potential; high faradaic efficiency | requiring precise catalyst design, scale-up challenges | [ |
| C-C bond | Ni catalyst + electroreduction | Reductive cross-coupling (aziridines + alkenyl bromides) | enantioselective, inexpensive metal | chiral ligands required, substrate-dependent | [ |
| Ni catalyst | Nozaki-Hiyama-Kishi coupling | first enantioselective electroreductive variant | halide-sensitive, ligand dependence | [ | |
| Fe, Ni, Ru, Rh catalysts | C1 → C2+ (from CO2/CH4/MeOH) | broadening carbonylation pathways | high energy input, low selectivity | [ | |
| C-N bond | Cu NPs | CO + NH3 → acetamide | inexpensive NP catalyst, decent selectivity | NP aggregation, instability | [ |
| Cu catalyst | CO2 + NH3 → formamide | high FE, stabilizing intermediates | poor stability, limited scale | [ | |
| Cu catalysts | CO2 + NO3-/NO2- → amines | access to multiple amines via intermediate pairing | low yield, multi-step intermediates | [ | |
| C-O bond | Pd (BrettPhos, RockPhos, etc.) | Aryl ether synthesis | ligand control enables selectivity and efficiency | costly ligands, sensitive to air/moisture | [ |
| Ni catalysts | C-O ether coupling | cheap Pd alternative, functional group tolerance | lower activity, catalyst deactivation | [ | |
| Cu catalysts + neutral ligands | Aryl-alkyl ethers | reducing alcohol excess, pharma relevance | ligand-dependent, recyclability issues | [ | |
| Mn(II) catalysts | Indole dearomatization with alcohols/NHTosylates (via Langlois’ reagent) | enabling electrochemical C-O cyclization; access to indolines | requiring specific nucleophiles; substrate limitations | [ |
Fig. 14. An overview of the oxidative amination processes that Ti imido (Ti≡NR) complexes catalyze or mediate. Reproduced with permission from Ref. [212]. Copyright 2021, American Chemical Society.
Fig. 15. (a) Known de-aromatization techniques: enzymatic arene dihydroxylation, arene-olefin meta-cycloaddition, and alkylative birch reduction. (b) Planar aromatic compounds undergoing de-aromatization to become saturated, structurally complicated frameworks. Reproduced with permission from Ref. [213]. Copyright 2021, John Wiley and Sons.
Fig. 16. (a) The schematic diagram shows the tuning of the nitrate reduction reaction for selective NH2OH production on the molecularly dispersed electro catalysts (MDEs) of metal phthalocyanine (MPc) supported on CNTs. (b) Electrocatalytic performance of ZnPc MDE for NO3-RR. Reproduced with permission from Ref. [214]. Copyright 2024, Springer Nature.
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