Direct solar-driven methane (CH₄) reforming is highly desirable but challenging, particularly to achieve a value-added product with high selectivity. Here, we identify a synergistic ensemble effect of atomically dispersed copper (Cu) species and partially reduced tungsten (W^δ+), stabilised over an oxygen-vacancy-rich WO₃, which enables exceptional photocatalytic CH₄ conversion to formaldehyde (HCHO) under visible light, leading to nearly 100% selectivity, a very high yield of 4979.0 μmol·g⁻¹ within 2 h, and the normalised mass activity of 8.5 × 10⁶ μmol·g^-1_Cu·h⁻¹ of HCHO at ambient temperature. In-situ EPR and XPS analyses indicate that the Cu species serve as the electron acceptor, promoting the photo-induced electron transfer from the conduction band to O₂, generating reactive •OOH radicals. In parallel, the adjacent W^δ+ species act as the hole acceptor and the preferred adsorption and activation site of H₂O to produce hydroxyl radicals (•OH), and thus activate CH₄ to methyl radicals (•CH₃). The synergy of the adjacent dual active sites boosts the overall efficiency and selectivity of the conversion process.

直接太阳能驱动的甲烷 (CH ₄ ) 重整是非常可取的，但具有挑战性，特别是要获得具有高选择性的增值产品。^{在这里，我们确定了原子分散的铜 (Cu) 物种和部分还原的钨 (W δ+} )的协同整体效应，稳定在富含氧空位的 WO ₃上，这使得在以下条件下能够将 CH ₄出色地光催化转化为甲醛 (HCHO)可见光，导致近100%的选择性，2小时内4979.0 μmol·g ⁻¹的非常高产率，以及8.5 × 10 ⁶  μmol·g ^-1 _Cu ·h ⁻¹的归一化质量活性环境温度下的 HCHO。原位EPR 和XPS 分析表明Cu 物种作为电子受体，促进光诱导电子从导带转移到O 2 _，​​产生反应性•OOH 自由基。同时，相邻的W ^δ+物种作为空穴受体和H ₂ O的优选吸附和活化位点产生羟基自由基（•OH），从而将CH ₄活化为甲基自由基（•CH ₃）。相邻双活性位点的协同作用提高了转化过程的整体效率和选择性。