Alkali cation effects in electrochemical carbon dioxide reduction

doi:10.1016/S1872-2067(25)64834-0

Abstract

Abstract:

In recent decades, the unabated consumption of fossil fuels has resulted in a sustained increase in carbon dioxide emissions, exacerbating environmental challenges typified by the greenhouse effect, which has underscored the urgent imperative to develop highly efficient carbon dioxide capture and utilization technologies. The electrocatalytic carbon dioxide reduction reaction (eCO₂RR) has emerged as a promising strategy for the conversion of CO₂ into high-value-added chemical commodities. Recent investigations have demonstrated that alkali cations played a pivotal role in eCO₂RR, encompassing enhancements in catalytic activity and modulations of product selectivity. Despite these advancements, how exactly the alkali cations affect the electrocatalytic reaction process and the key determinants of alkali cation effects remain subjects of ongoing debate. We analyzed current research on the effects of alkali cations, in which the concentration and type of alkali cations were generally correlated with eCO₂RR performance. However, the distribution of alkali cations at the electrode interface is often overlooked. In this study, we first conclude recent advancements in electric double layer theory and elucidate three distinct modes of alkali cation distribution at the electrode-electrolyte interface. Subsequently, we systematically summarize the specific mechanisms through which these cations operate in different electrolyte systems. Furthermore, we propose fundamental perspectives for future investigations into alkali cation effects, aiming to provide guiding principles for the rational design of next-generation advanced eCO₂RR electrolysis systems.

Key words: Electrocatalysis, Carbon dioxide reduction reaction, Alkali cation effects, Electrode interfacial distribution, Adsorption mode

Jiaqi Xiang, Limiao Chen, Shanyong Chen, You-Nian Liu. Alkali cation effects in electrochemical carbon dioxide reduction[J]. Chinese Journal of Catalysis, 2026, 80: 38-58.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64834-0

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Figures/Tables 12

Fig. 1. Schematic illustration of the EDL structure in the GCS model and the distribution of different adsorbed alkali cations. The white, red, blue and gray spheres represent hydrogen, oxygen, metal and carbon atoms, respectively.

Fig. 2. (a) 3D view of the proposed (2 × 2) ball model at ?850 mV (left) and density profiles of the four layers (α ? δ) on Pt(111) surface obtained from the fits (right). Pt atom, gray balls; Cs+ ions, blue balls; The red and pink balls represent the water molecules. Reprinted with permission [64]. Copyright 2018, American Chemical Society. (b) Schematic diagram of adsorption model for specific adsorption alkali cations on electrode surface. Reprinted with permission [70]. Copyright 2021, American Chemical Society. (c) Solvated surface structures on Pt(111) in 3 × 3 unit cell. White, H atom; Red, O atom; Green, Ba2+ ions; Purple, Na+ ions; Blue, Pt atom. Reprinted with permission [73]. Copyright 2014, Royal Society of Chemistry. (d) A schematic illustration of the interface structure at the negatively charged (left) and positively charged (right) surface. Alkali cations on positively charged surface have a quasispecific adsorption configuration. Reprinted with permission [68]. Copyright 2011, Elsevier. B.V.

Table 1 The comparison of the effects of alkali cations on the catalytic eCO2RR performance.

Catalyst	Electrolyte	FE_CO^a (%)	FE_HCOOH^a (%)	FE_CH4 ^a (%)	FE_C2H4^a (%)	FE_C2H5OH ^a (%)	Ref.
Cu	1.0 mol L^‒1 H₃PO₄	<1	<1	<1	<1	—^b	[44]
Cu	1.0 mol L^‒1 H₃PO₄ + 3.0 mol L^‒1 KCl	~5	~7	~20	~10	—	[44]
Cu	H₃PO₄ + 2 mmol L^‒1 K⁺ (pH 2)	~10 (C₁)			~2 (C₂)		[48]
Cu	H₃PO₄ + 0.2 mol L^‒1 K⁺ (pH 2)	~22 (C₁)			~10 (C₂)		[48]
CuO-derived Cu	1.0 mol L^‒1 KHCO₃	~10	—	~1	~42	—	[52]
CuO-derived Cu	1.0 mol L^‒1 KHCO₃ + 1.0 mol L^‒1 CTAB	~1	—	~1	~5	—	[52]
SnO₂/C	0.1 mol L^‒1 HOTf + 0.4 mol L^‒1 LiOTf	~5	~20	—	—	—	[69]
SnO₂/C	0.1 mol L^‒1 HOTf + 0.4 mol L^‒1 CsOTf	~4	~85	—	—	—	[69]
NiPc/CNT	H₂SO₄ + 3.0 mol L^‒1 KCl (pH 1)	65.9	—	—	—	—	[78]
NiPc/CNT-SO₃H	H₂SO₄ + 3.0 mol L^‒1 KCl (pH 1)	92.7	—	—	—	—	[78]
CuAg/GDL	0.5 mol L^‒1 KOH	~30	—	~5.5	~22	—	[83]
	1.0 mol L^‒1 KOH	~25	—	~7.5	~30	—
	2.0 mol L^‒1 KOH	~10	—	~10	~20	—
Ag	0.1 mol L^‒1 LiHCO₃	55.8	—	—	—	—	[84]
	0.1 mol L^‒1 KHCO₃	85.4	—	—	—	—
	0.1 mol L^‒1 CsHCO₃	90.2	—	—	—	—
Cu	0.1 mol L^‒1 LiHCO₃	—	—	11.1	6.7	~4
	0.1 mol L^‒1 KHCO₃	—	—	13.5	31.5	9.0
	0.1 mol L^‒1 CsHCO₃	—	—	12.9	39.6	9.7
Cu	H₂SO₄ + 0.5 mol L^‒1 K₂SO₄ (pH 2)	—	—	~10	—	—	[85]
Cu + 18-Crown-6 (1:1)	H₂SO₄ + 0.5 mol L^‒1 K₂SO₄ (pH 2)	—	—	~25	—	—
Cu + 18-Crown-6 (1:3)	H₂SO₄ + 0.5 mol L^‒1 K₂SO₄ (pH 2)	—	—	51.2	—	—
IL−Ni−NC	H₂SO₄ (pH 1.7)	~67	—	—	—	—	[86]
IL−Ni−NC	H₂SO₄ + 1.0 mol L^‒1 K⁺ (pH 1.7)	~90	—	—	—	—
Ag	H₂SO₄ (pH 1.7)	~10	—	—	—	—
Ag	H₂SO₄ + 1.0 mol L^‒1 K⁺ (pH 1.7)	~30	—	—	—	—
Au	0.1 mol L^‒1 Li₂SO₄ (pH 3)	~47	—	—	—	—	[87]
Au	0.1 mol L^‒1 K₂SO₄ (pH 3)	~70	—	—	—	—	[87]
Ag	0.1 mol L^‒1 H₂SO₄ + 0.2 mol L^‒1 K₂SO₄	~60	—	—	—	—	[88]
Ag + PSS	0.1 mol L^‒1 H₂SO₄ + 0.2 mol L^‒1 K₂SO₄	~94	—	—	—	—	[88]
NiPc-OMe MDE	0.1 H₂SO₄	0	—	—	—	—	[89]
	0.1 mol L^‒1 H₂SO₄ + 0.1 mol L^‒1 K₂SO₄	~80	—	—	—	—
	0.1 mol L^‒1 H₂SO₄ + 0.4 mol L^‒1 K₂SO₄	~100	—	—	—	—

Table 1 The comparison of the effects of alkali cations on the catalytic eCO2RR performance.

Catalyst	Electrolyte	FE_CO^a (%)	FE_HCOOH^a (%)	FE_CH4 ^a (%)	FE_C2H4^a (%)	FE_C2H5OH ^a (%)	Ref.
Cu	1.0 mol L^‒1 H₃PO₄	<1	<1	<1	<1	—^b	[44]
Cu	1.0 mol L^‒1 H₃PO₄ + 3.0 mol L^‒1 KCl	~5	~7	~20	~10	—	[44]
Cu	H₃PO₄ + 2 mmol L^‒1 K⁺ (pH 2)	~10 (C₁)			~2 (C₂)		[48]
Cu	H₃PO₄ + 0.2 mol L^‒1 K⁺ (pH 2)	~22 (C₁)			~10 (C₂)		[48]
CuO-derived Cu	1.0 mol L^‒1 KHCO₃	~10	—	~1	~42	—	[52]
CuO-derived Cu	1.0 mol L^‒1 KHCO₃ + 1.0 mol L^‒1 CTAB	~1	—	~1	~5	—	[52]
SnO₂/C	0.1 mol L^‒1 HOTf + 0.4 mol L^‒1 LiOTf	~5	~20	—	—	—	[69]
SnO₂/C	0.1 mol L^‒1 HOTf + 0.4 mol L^‒1 CsOTf	~4	~85	—	—	—	[69]
NiPc/CNT	H₂SO₄ + 3.0 mol L^‒1 KCl (pH 1)	65.9	—	—	—	—	[78]
NiPc/CNT-SO₃H	H₂SO₄ + 3.0 mol L^‒1 KCl (pH 1)	92.7	—	—	—	—	[78]
CuAg/GDL	0.5 mol L^‒1 KOH	~30	—	~5.5	~22	—	[83]
	1.0 mol L^‒1 KOH	~25	—	~7.5	~30	—
	2.0 mol L^‒1 KOH	~10	—	~10	~20	—
Ag	0.1 mol L^‒1 LiHCO₃	55.8	—	—	—	—	[84]
	0.1 mol L^‒1 KHCO₃	85.4	—	—	—	—
	0.1 mol L^‒1 CsHCO₃	90.2	—	—	—	—
Cu	0.1 mol L^‒1 LiHCO₃	—	—	11.1	6.7	~4
	0.1 mol L^‒1 KHCO₃	—	—	13.5	31.5	9.0
	0.1 mol L^‒1 CsHCO₃	—	—	12.9	39.6	9.7
Cu	H₂SO₄ + 0.5 mol L^‒1 K₂SO₄ (pH 2)	—	—	~10	—	—	[85]
Cu + 18-Crown-6 (1:1)	H₂SO₄ + 0.5 mol L^‒1 K₂SO₄ (pH 2)	—	—	~25	—	—
Cu + 18-Crown-6 (1:3)	H₂SO₄ + 0.5 mol L^‒1 K₂SO₄ (pH 2)	—	—	51.2	—	—
IL−Ni−NC	H₂SO₄ (pH 1.7)	~67	—	—	—	—	[86]
IL−Ni−NC	H₂SO₄ + 1.0 mol L^‒1 K⁺ (pH 1.7)	~90	—	—	—	—
Ag	H₂SO₄ (pH 1.7)	~10	—	—	—	—
Ag	H₂SO₄ + 1.0 mol L^‒1 K⁺ (pH 1.7)	~30	—	—	—	—
Au	0.1 mol L^‒1 Li₂SO₄ (pH 3)	~47	—	—	—	—	[87]
Au	0.1 mol L^‒1 K₂SO₄ (pH 3)	~70	—	—	—	—	[87]
Ag	0.1 mol L^‒1 H₂SO₄ + 0.2 mol L^‒1 K₂SO₄	~60	—	—	—	—	[88]
Ag + PSS	0.1 mol L^‒1 H₂SO₄ + 0.2 mol L^‒1 K₂SO₄	~94	—	—	—	—	[88]
NiPc-OMe MDE	0.1 H₂SO₄	0	—	—	—	—	[89]
	0.1 mol L^‒1 H₂SO₄ + 0.1 mol L^‒1 K₂SO₄	~80	—	—	—	—
	0.1 mol L^‒1 H₂SO₄ + 0.4 mol L^‒1 K₂SO₄	~100	—	—	—	—

Fig. 3. (a) FE distribution of the major products H2, C2H4 and CO during operation at constant voltage (3.2 V) as a function of anolyte concentration. Reprinted with permission [92]. Copyright 2023, Springer Nature. (b) Structures and energetics for the free CO2 reactant, transition state, and product *CO2- during adsorption in 1 mol L?1 KOH (left) and 2 mol L?1 KOH (right) solutions on Au(111). The solid black curve corresponds to free and linear reactant CO2 in solution. The solid red and green curves correspond to product *CO2- energies taken with respect to the reference state in 1 mol L?1 KOH and 2 mol L?1 KOH, respectively. The dotted red and green curves correspond to the energies of the transition state taken with respect to the reference state for the initial electron transfer in 1 mol L?1 KOH and 2 mol L?1 KOH solutions at the Au(111) cathode, respectively. Reprinted with permission [80]. Copyright 2023, American Chemical Society. FECH4 (c) and FEC2H4 (d) with different concentration of K+ at ?0.8 V. (e) ΔECOad contract with the concentration of interfacial K+. Reprinted with permission [83]. Copyright 2025, Elsevier. (f) Cation effects on the standard free energies of two elementary steps. (g,h) Influence of cation concentration on the elementary steps of the CORR. Reprinted with permission [53]. Copyright 2024, Springer Nature.

Fig. 4. (a) pKa of hydrolysis of hydrated Li+ and Cs+ on the surface of Ag electrode and its effect on the distribution of pH and CO2 concentration. Reprinted with permission [84]. Copyright 2016, American Chemical Society. (b) Interaction between H3O+ and alkali metal cations. H3O+ and K+ are highlighted and shown as spheres where O is represented in red, H in white, and K in purple. Reprinted with permission [94]. Copyright 2024, Springer Nature. (c) Profile of βDFT with reference to EDL width from different transition state models of *CO2- formation with explicit K+ and H2O. The dash black line represents βexp = 0.44 on Au(111) surface in 0.1 mol L?1 KHCO3. The blue solid line is the profile of βDFT for the simple *CO2- model. The red solid and dashed lines represent the profiles of βDFT for the coadsorbed cation models, respectively. The purple solid and dashed lines represent the profiles of βDFT for the coordinated cation model, respectively. (d) β derived from Tafel plots of eCO2RR to CO as a function of cation identity. Reprinted with permission [46]. Copyright 2025, American Association for the Advancement of Science. (e) Free energy profiles and representative structures at initial state (IS), transition state (TS), and final state (FS) for CO2 adsorption with different alkali cations (Li+, Na+, K+ and Cs+). Reprinted with permission [94]. Copyright 2024, Springer Nature. (f) The schematic diagram of reaction mechanism changes of eCO2RR on Ni?N4 catalyst with and without K+. Reprinted with permission [97]. Copyright 2024, Springer Nature.

Fig. 5. (a) Comparison of simulated XANES spectra of Ni?N4 and Ni-N4-COOH. (b) Normalized in-situ nickel K-edge XANES spectra of Ni-N4-HM in CO2 saturated 1 mol L?1 KHCO3 buffer at different applied potentials. (c) The radial distribution function g(r) and the corresponding integrated coordination number of the O?K+ pair in an equilibrated AIMD trajectory. (d) Evolution of the Ni?C distance, O?C?O angle, and K-O (CO2) distance before and after the K+ ion left the active site. Reprinted with permission [97]. Copyright 2024, Springer Nature. (e) Different products (C2H4, C2H5OH, CH4 and CO) as a function of applied potential for O2-plasma-activated Cu sample measured in different electrolytes after 1 h of CO2RR. Reprinted with permission [77]. Copyright 2018, American Chemical Society.

Fig. 6. (a) Schematics of the migration of cations toward the Cu surface. Reprinted with permission [51]. Copyright 2024, American Chemical Society. (b) Schematic representation of the integrated mechanism elucidating the cation-dependent C2+ selectivity. Reprinted with permission [99]. Copyright 2024, American Chemical Society. (c) Illustrations of the different mechanistic proposals of cation effects on enhancing C?C coupling. Reprinted with permission [52]. Copyright 2024, American Chemical Society.

Fig. 7. Profiles of potential (a) and electric field strength (b) with and without K+. (c) Schemata of double layer near cathode. Grey, red, white, blue, yellow and orange spheres represent C, O, H, K, F and S atoms, respectively. Orange arrows represent electric field (E) generated by the cathode, and blue arrows represent E generated by cations at OHP. μ represents the dipole moment of the adsorbed CO2 intermediate. Reprinted with permission [69]. Copyright 2022, Springer Nature. (d) Simulated electric field strength over the distance from outer Helmholtz plane (OHP). In situ Raman spectra of (e) Cu and (f) crown ether-modified Cu catalysts under applied potentials. Reprinted with permission [85]. Copyright 2023, Wiley-VCH.

Fig. 8. (a) Schematics of three water structures, including 4H?H2O, 2H?H2O, and K?H2O. Reprinted with permission [106]. Copyright 2024, American Chemical Society. (b) The variation trend of three types of water populations. (c) The experimental frequencies of the O?H stretching mode of different interfacial water. Reprinted with permission [78]. Copyright 2025, American Institute of Chemical Engineers. (d) In-situ ATR-SEIRAS spectra of IL-Ni-NC in the 0.05 mol L?1 K2SO4 + H2SO4 (pH 1.7, 2.1, and 4.0). (e) Water structure ratio of pH 1.7 (up) and pH 4.0 (down) with Fig. 8(d). Reprinted with permission [86]. Copyright 2025, Elsevier. (f) The dependence of band intensity of adsorbed *CO2 on cation concentration. (g) Cation concentration (c)-dependent partial current of CO from the eCO2RR. (h) Schematic presentation of water network around Li+ and Na+ and its interactions with adsorbed CO2. Reprinted with permission [45]. Copyright 2024, Springer Nature.

Fig. 9. (a) Effects of physically adsorbed K+ on the migration of H+. Reprinted with permission [107]. Copyright 2023, Springer Nature. (b) Schemata of hydrated K+ inhibits the migration of H+. (c) ATR-SEIRAS spectra of *COatop region as a function of potential and the calculated Stark tuning slopes for 2-200 mmol L-1 K+. (d) eCO2RR electrolysis product distribution for different K+ concentration in H3PO4 (pH = 2). (e) Interfacial pH as a function of time for different K+ concentration. (f) Time-dependent *CO band intensity for Fig. 9(e). Reprinted with permission [48]. Copyright 2024, American Chemical Society.

Fig. 10. (a) Schematic representation of the interactions of the cations with the negatively charged *CO2- intermediates together with the reaction mechanism. Reprinted with permission [108]. Copyright 2021, Springer Nature. (b) Reaction energy barriers of *CO dimerization on different slabs. IS, initial state. TS, transition state. FS, final state. Reprinted with permission [109]. Copyright 2022, Springer Nature. (c) Representative snapshots from MD simulations showing different solvation structures near the Li+ and the adsorbed *CHO intermediate. Reprinted with permission [47]. Copyright 2024, Springer Nature. (d) Time-dependent product distributions and partial current densities of sputtered Cu at ?1.3 VRHE. (e) Cs+ concentration-dependent product distributions and partial current densities of sputtered Cu at ?1.2 VRHE. (f) ATR-SEIRAS spectra of sputtered Cu at various applied potentials in CO2-saturated 0.5 mol L-1 M2SO4 (M = Li, K, and Cs). Reprinted with permission [110]. Copyright 2025, American Chemical Society.

Fig. 11. (a) Possible *COads coupling mechanism on Cu(100). Reprinted with permission [111]. Copyright 2021, PNAS license. (b) Schematic illustration of the interpretation of spectra. In the absence of K+, hydrated methyl4N+ accumulates in the EDL with decreasing potential. In the presence of K+, methyl4N+ads is displaced by Kads. Kads is indicated by grey patterned circles. Blue and orange arrows indicate decreasing electrode potential (U). Reprinted with permission [50]. Copyright 2022, Springer Nature. (c) Schematic of c-PDDA decorated catalyst. The blue lines represent the polymer chains, and the short red lines represent the ?(CH2)6? cross-linkers. Reprinted with permission [107]. Copyright 2023, Springer Nature. (d) MD model predictions of atomic configurations for the Cu/CG systems. Red, grey, yellow, green, purple, blue and white balls represent O, C, Cu, Cl, K, N and H, respectively. Reprinted with permission [112]. Copyright 2023, Springer Nature.

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