Junting Feng

The reverse water gas shift (RWGS) efficiently mitigates CO ₂ emissions and produces syngas, but the low‐temperature activity‐selectivity trade‐off persists. Herein, a novel NiFe‐NiIn‐X dual‐phase alloy catalyst was fabricated via high‐temperature reduction of LDH precursors with phase engineering to boost RWGS. Unlike single‐phase NiFe or NiIn, this phase‐engineered dual‐alloy nanostructure effectively isolates Ni sites, forms a heteroalloy interface, and promotes charge transfer among Ni, Fe, and In. This enhances CO ₂ adsorption and activation and weakens H* and CO* adsorption, suppressing methane and promoting CO. At 300°C and ambient pressure, optimized NiFe‐NiIn‐0.2 exhibited 15.1% CO ₂ conversion, 98.9% CO selectivity, and stable operation over 100 h. This study illustrates how phase engineering of LDH‐derived alloys can effectively decouple the low‐temperature activity‐selectivity trade‐off in the RWGS reaction, providing a promising strategy for the rational design of low‐temperature RWGS catalysts.

The thermodynamic−kinetic origin of why alloying is a prerequisite for interstitial carbon playing a promotional role in selective acetylene hydrogenation over Ni-based catalysts remains elusive. Moreover, catalytic mechanisms are frequently studied on pristine or bare surface models, overlooking the realistic surface states and coverage effects under operando conditions. Herein, we establish a realistic surface-state research paradigm, integrating global optimization, ab initio thermodynamic phase diagrams, constrained ab initio molecular dynamics, and coverage self-consistent calculations. We reveal that pure Ni thermodynamically rejects subsurface carbon (ΔEinc = −0.41 eV) with a prohibitively high kinetic barrier (3.75 eV), while Ga/Zn alloying switches the thermodynamics to favorable (ΔEinc = −3.61 eV) and lowers the penetration barrier by ∼0.95 eV via lattice expansion and electronic activation. Coverage-dependent calculations demonstrate that adsorbate−adsorbate interactions adjust the free energy profiles, and the coverage self-consistent microkinetic modeling and reactor simulations align well with experimental trends of Ni-based catalysts. The excellent performance of Ni3GaCx and Ni3ZnCx originates from interstitial carbon within the alloy matrix. Synergistic ligand and geometric effects tuning Ni-based carbic to the summit of a predictive selectivity volcano that simultaneously suppresses overhydrogenation and oligomerization, where electronic modulation optimizes intermediate adsorption strength while adjacent Ni atoms stretching creates selective advantage sites. This work transforms the understanding of interstitial carbon from a phenomenological observation into a quantitative, descriptor-based design map that can guide future rational catalyst design via controlled interstitial modification engineering.

To address the challenge of removing water from dehydration reactions when reaction components share similar physical properties with water, we developed a reaction coupling strategy that integrates dehydration with the water‐gas shift (WGS) which was enabled by the Pt/hydrophobically modified Al‐SBA catalyst (Pt/Al‐SBA‐C ₁₂ ). Through quasi in situ characterizations and molecular dynamics simulations, the dynamic evolution process of water generation, transport, and activation has been elucidated. At the Lewis acid sites on the hydrophobic SBA surface, lactic acid, and alcohol molecules react to form esters and water. Subsequently, driven by the wettability gradient, water molecules undergo directional transport from the SBA surface to the Pt sites within 7.5 ns, accompanied by the induction of contact electrification. The dissociated ^* OH over Pt sites further reacts with adsorbed CO to form an ^* COOH intermediate, ultimately producing CO ₂ and H ₂ . Leveraging this system, the Pt/Al‐SBA‐C ₁₂ catalyst achieves a lactic acid conversion of 96.1% in the coupled reaction, substantially higher than the 52.3% attained by unmodified Pt/Al‐SBA under standalone esterification conditions. Moreover, the Pt/Al‐SBA‐C ₁₂ catalyst maintains stable performance over at least 10 cycles. With broad substrate applicability, our approach enables water removal without relying on differences in physical properties, showing great potential for practical applications.

To address the challenge of removing water from dehydration reactions when reaction components share similar physical properties with water, we developed a reaction coupling strategy that integrates dehydration with the water‐gas shift (WGS) which was enabled by the Pt/hydrophobically modified Al‐SBA catalyst (Pt/Al‐SBA‐C ₁₂ ). Through quasi in situ characterizations and molecular dynamics simulations, the dynamic evolution process of water generation, transport, and activation has been elucidated. At the Lewis acid sites on the hydrophobic SBA surface, lactic acid, and alcohol molecules react to form esters and water. Subsequently, driven by the wettability gradient, water molecules undergo directional transport from the SBA surface to the Pt sites within 7.5 ns, accompanied by the induction of contact electrification. The dissociated ^* OH over Pt sites further reacts with adsorbed CO to form an ^* COOH intermediate, ultimately producing CO ₂ and H ₂ . Leveraging this system, the Pt/Al‐SBA‐C ₁₂ catalyst achieves a lactic acid conversion of 96.1% in the coupled reaction, substantially higher than the 52.3% attained by unmodified Pt/Al‐SBA under standalone esterification conditions. Moreover, the Pt/Al‐SBA‐C ₁₂ catalyst maintains stable performance over at least 10 cycles. With broad substrate applicability, our approach enables water removal without relying on differences in physical properties, showing great potential for practical applications.

Coupling hydrogenation and dehydrogenation is of great significance, as both are pivotal bond reconstruction modes and co‐occur in about 10% of chemical syntheses. However, stoichiometric imbalance often necessitates exogenous hydrogen, which causes “seesaw effect” and inhibits dehydrogenation, challenging thermodynamics and kinetics of tandem process. Herein, we propose a dynamic strategy based on chemical looping to modulate hydrogen species. We designed Ru _n @NiCu‐V _M catalyst with metal vacancy (V _M ) induced “electron allocator” properties, enabling reversible electron capture and release via chemical looping, which drives the neutral H· to convert into H ⁻ &H ⁺ , while simultaneously completing electron cycling. The converted H ⁻ &H ⁺ promote hydrogenation of polar ─C═N bonds in the tandem reaction of 5‐hydroxymethylfurfural to 2,5‐furandimethanamine, while neutral H· enhances the dehydrogenation rate by avoiding charge repulsion with H ⁻ &H ⁺ generated from dehydrogenation of ─CH ₂ OH. The coupled hydrogenation‐dehydrogenation process achieves a 1.7‐fold rate enhancement, delivers 92% 2,5‐furandimethanamine yield, outperforms most reported catalysts, and exhibits broad substrate applicability.

Coupling hydrogenation and dehydrogenation is of great significance, as both are pivotal bond reconstruction modes and co‐occur in about 10% of chemical syntheses. However, stoichiometric imbalance often necessitates exogenous hydrogen, which causes “seesaw effect” and inhibits dehydrogenation, challenging thermodynamics and kinetics of tandem process. Herein, we propose a dynamic strategy based on chemical looping to modulate hydrogen species. We designed Ru _n @NiCu‐V _M catalyst with metal vacancy (V _M ) induced “electron allocator” properties, enabling reversible electron capture and release via chemical looping, which drives the neutral H· to convert into H ⁻ &H ⁺ , while simultaneously completing electron cycling. The converted H ⁻ &H ⁺ promote hydrogenation of polar ─C═N bonds in the tandem reaction of 5‐hydroxymethylfurfural to 2,5‐furandimethanamine, while neutral H· enhances the dehydrogenation rate by avoiding charge repulsion with H ⁻ &H ⁺ generated from dehydrogenation of ─CH ₂ OH. The coupled hydrogenation‐dehydrogenation process achieves a 1.7‐fold rate enhancement, delivers 92% 2,5‐furandimethanamine yield, outperforms most reported catalysts, and exhibits broad substrate applicability.

Water removal is one of the fundamental and energy‐intensive processes widely involved in modern industries. Massive energy input has been considered necessary to break the water‐substrate affinity but causes high energy consumption and challenges the stability of the substrates. In this study, we developed a reaction‐coupled water removal strategy to chemically disrupt the water‐substrate affinity and adopted it to the water desorption of 4A zeolite desiccant. This approach avoided the necessity for high energy input and thus achieved fast water desorption at a temperature as low as 130°C (1.87 mmol _H2O /[g _zeo min]) when coupled with the water‐gas shift (WGS) reaction. Comprehensive theoretical and experimental studies revealed that water molecules at confined cationic sites can be distorted and activated by strong interactions (H‐O…Na ⁺ ) and weak interactions (H‐bond and spatial constraints). Concurrently, the exothermic WGS reaction provided in situ thermal compensation to the endothermic water desorption, reducing the total heat input by 40%, as determined by microcalorimetry.