Currently,　10　million　tons　of　coal　to　ethylene　glycol　(CTEG)　plants　have　been　built　in　China.　Due　to　the　poor　market　conditions　of　ethylene　glycol,　many　plants　are　in　a　state　of　shutdown　and　are　in　urgent　need　of　transformation.　CO　esterification　in　CTEG　can　produce　two　important　ester　chemicals,　dimethyl　oxalate　(DMO)　and　dimethyl　carbonate　(DMC).　Converting　the　product　DMO　into　higher　value-added　DMC　is　one　of　the　transition　ideas.　DMO　can　be　converted　to　DMC　by　decarbonylation,　but　new　reactors　and　catalysts　are　needed.　It　would　be　more　economical　and　challenging　to　utilize　CTEG　plant　to　produce　DMC　directly　by　replacing　the　catalyst　with　a　new　one.　Pd/α-Al2O3　is　the　traditional　catalyst　for　DMO　production.　In　this　work,　we　proposed　a　PdZn　alloying　strategy　to　modulate　the　selectivity　of　CO　esterification　products,　and　realize　the　product　selectivity　change　from　DMO　to　DMC.　Compared　with　Pd/α-Al2O3,　the　selectivity　to　DMO　over　PdZn(1:4)/α-Al2O3　was　significantly　decreased　(85.8%→16.8%),　and　the　DMC　selectivity　was　increased　remarkably　(14.2%→83.2%).　The　formation　of　PdZn　alloy　was　demonstrated　by　X-ray　diffraction　(XRD),　transmission　electron　microscope　(TEM),　and　other　characterizations,　X-ray　photoelectron　spectroscopy　(XPS)　results　showed　that　the　alloy　formed　between　Zn　and　Pd　significantly　changed　the　electron　density　of　the　Pd　component,　and　the　Pd　component　was　in　an　electron-deficient　state,　which　was　conducive　to　the　improvement　of　the　performance　of　the　DMC　reaction.　In　addition,　the　results　of　CO　diffused　reflectance　infrared　Fourier　transform　spectroscopy　(DRIFTS)　characterization　showed　that　Zn　can　disperse　Pd.　With　the　increase　of　the　second　metal　Zn　content,　the　continuous　Pd　metal　phase　disappears,　and　an　isolated　single-atom　alloy　state　may　be　formed,　which　inhibits　the　formation　of　the　byproduct　DMO.　The　present　study　not　only　provides　a　new　way　to　regulate　the　selectivity　of　CO　esterification　products,　but　also　provides　an　idea　for　the　conversion　of　CTEG　plants.　©　2025　Shanghai　Institute　of　Organic　Chemistry,　Chinese　Academy　of　Sciences.